Rare-earth metal gallium silicides via the gallium self-flux method. Synthesis, crystal structures, and magnetic properties of RE(Ga 1–xSi x)₂ (RE=Y, La–Nd, Sm, Gd–Yb, Lu)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darone, Gregory M.; Hmiel, Benjamin; Zhang, Jiliang

Fifteen ternary rare-earth metal gallium silicides have been synthesized using molten Ga as a molten flux. They have been structurally characterized by single-crystal and powder X-ray diffraction to form with three different structures—the early to mid-late rare-earth metals RE=La–Nd, Sm, Gd–Ho, Yb and Y form compounds with empirical formulae RE(Ga xSi 1–x)₂ (0.38≤x≤0.63), which crystallize with the tetragonal α-ThSi₂ structure type (space group I4₁/amd, No. 141; Pearson symbol tI12). The compounds of the late rare-earth crystallize with the orthorhombic α-GdSi₂ structure type (space group Imma, No. 74; Pearson symbol oI12), with refined empirical formula REGa xSi 2–x–y (RE=Ho, Er, Tm;more » 0.33≤x≤0.40, 0.10≤y≤0.18). LuGa₀.₃₂₍₁₎Si₁.₄₃₍₁₎ crystallizes with the orthorhombic YbMn₀.₁₇Si₁.₈₃ structure type (space group Cmcm, No. 63; Pearson symbol oC24). Structural trends are reviewed and analyzed; the magnetic susceptibilities of the grown single-crystals are presented. - Graphical abstract: This article details the exploration of the RE–Ga–Si ternary system with the aim to systematically investigate the structural “boundaries” between the α-ThSi₂ and α-GdSi₂-type structures, and studies of the magnetic properties of the newly synthesized single-crystalline materials. Highlights: • Light rare-earth gallium silicides crystallize in α-ThSi₂ structure type. • Heavy rare-earth gallium silicides crystallize in α-GdSi₂ structure type. • LuGaSi crystallizes in a defect variant of the YbMn₀.₁₇Si₁.₈₃ structure type.« less

Synthesis, growth, structure, mechanical and optical properties of a new semi-organic 2-methyl imidazolium dihydrogen phosphate single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagapandiselvi, P., E-mail: nagapandiselvip@ssn.edu.in; Baby, C.; Gopalakrishnan, R.

2016-09-15

Highlights: • 2MIDP crystals were grown by slow evaporation solution growth technique. • Single crystal XRD revealed self-assembled supramolecular framework. • Z scan technique is employed for third order nonlinear optical susceptibility. • Structure-property correlation is established. - Abstract: A new semi-organic compound, 2-methyl imidazolium dihydrogen phosphate (2MIDP), was prepared and good quality single crystals of 2MIDP were grown by slow evaporation solution growth technique. Crystal structure elucidated using Single crystal XRD showed that 2MIDP crystallizes in monoclinic system with P2{sub 1}/c space group. FT-IR, UV-Vis-NIR, Fluorescence and FT-NMR spectra confirm the molecular structure of 2MIDP. The UV-Vis-NIR spectra establishedmore » the suitability of the compound for NLO applications. TG-DSC showed that 2MIDP is thermally stable up to 200 °C. Mechanical characteristics like hardness number (H{sub v}), stiffness constant (C{sub 11}), yield strength (σ{sub v}), fracture toughness (K{sub c}) and brittleness index (B{sub i}) were assessed using Vicker’s microhardness tester. Third order nonlinear optical properties determined from Z-scan measurement using femto and picosecond lasers showed two photon reverse saturable absorption. The enhancement of nonlinear optical properties in femto second laser, revealed the suitability of 2MIDP for optical limiting applications.« less

Structural and optical effects induced by gamma irradiation on NdPO{sub 4}: X-ray diffraction, spectroscopic and luminescence study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sadhasivam, S.; Rajesh, N.P., E-mail: rajeshnp@hotmail.com

2016-02-15

Highlights: • Inorganic NdPO{sub 4} crystal was grown first time using potassium polyphosphate (K{sub 6}P{sub 4}O{sub 13}) flux. • NdPO{sub 4} crystal is insoluble in water, non-hygroscopic and high radiation resistance favoring for actinides host. • Actinide immobilization can be made at 1273 K. • High yield of 1061 nm photon emission. - Abstract: Rare earth orthophosphate (NdPO{sub 4}) monazite single crystals were grown using high temperature flux growth method employing K{sub 6}P{sub 4}O{sub 13} (K{sub 6}) as molten solvent. Their structural parameters were studied using single crystal X-ray diffraction (XRD) method. The grown crystals were examined by SEM andmore » EDX techniques for their homogeniousity and inclusion in the crystals. The influence of gamma irradiation in structural and optical absorption properties were studied by the powder XRD, FTIR and reflectance spectroscopy. The effect of gamma irradiation on luminescence properties was recorded. No significant structural change is observed up to 150 kGy gamma dose. The gamma ray induced charge trap in the crystal was saturated to 40 kGy dose. The luminescence intensity decreases with an increase in the irradiation. The emission of luminescence intensity stabilizes above 40 kGy gamma dose.« less

Experimental and theoretical investigations of non-centrosymmetric 8-hydroxyquinolinium dibenzoyl-(L)-tartrate methanol monohydrate single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sudharsana, N.; Krishnakumar, V.; Nagalakshmi, R., E-mail: nagaphys@yahoo.com

Graphical abstract: ORTEP diagram of HQDBT. - Highlights: • Single crystal XRD and NMR studies confirm the formation of the title compound. • SHG efficiency was found to be 0.6 times that of KDP. • First-order hyperpolarizability (β) was calculated using HF and B3LYP methods. - Abstract: A novel 8-hydroxyquinolinium dibenzoyl-(L)-tartrate methanol monohydrate crystal has been grown by slow evaporation technique. The single crystal X-ray diffraction analysis has been done for the title compound and is found to crystallize in orthorhombic space group P2{sub 1}2{sub 1}2{sub 1}. The optical absorption cut-off wavelength is found to be 440 nm. The vibrationalmore » analysis has been carried out to assess the functional groups present in the title compound. The molecular structure of the title compound has been confirmed by nuclear magnetic resonance spectroscopy. Thermogravimetric, differential scanning calorimetric and differential thermal analyses reveal the melting point and thermal stability of the title compound. The second harmonic generation efficiency is confirmed by Kurtz–Perry powder technique. Further quantum chemical calculations are performed using Gaussian 03 software.« less

Crystal structure of the Rasputin NTF2-like domain from Drosophila melanogaster

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vognsen, Tina, E-mail: tv@farma.ku.dk; Kristensen, Ole, E-mail: ok@farma.ku.dk

2012-03-30

Highlights: Black-Right-Pointing-Pointer The crystal structure of the NTF2-like domain of Rasputin protein is presented. Black-Right-Pointing-Pointer Differences to known ligand binding sites of nuclear transport factor 2 are discussed. Black-Right-Pointing-Pointer A new ligand binding site for the Rasputin and G3BP proteins is proposed. -- Abstract: The crystal structure of the NTF2-like domain of the Drosophila homolog of Ras GTPase SH3 Binding Protein (G3BP), Rasputin, was determined at 2.7 A resolution. The overall structure is highly similar to nuclear transport factor 2: It is a homodimer comprised of a {beta}-sheet and three {alpha}-helices forming a cone-like shape. However, known binding sites formore » RanGDP and FxFG containing peptides show electrostatic and steric differences compared to nuclear transport factor 2. A HEPES molecule bound in the structure suggests a new, and possibly physiologically relevant, ligand binding site.« less

Study of structural and optical properties of YAG and Nd:YAG single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kostić, S.; Lazarević, Z.Ž., E-mail: lzorica@yahoo.com; Radojević, V.

2015-03-15

Highlights: • Transparent YAG and pale pink Nd:YAG single crystals were produced by the Czochralski technique. • Growth mechanisms and shape of the liquid/solid interface and incorporation of Nd{sup 3+} were studied. • The structure of the crystals was investigated by X-ray diffraction, Raman and IR spectroscopy. • The 15 Raman and 17 IR modes were observed. • The obtained YAG and Nd:YAG single crystals were without core and of good optical quality. - Abstract: Yttrium aluminum garnet (YAG, Y{sub 3}Al{sub 5}O{sub 12}) and yttrium aluminum garnet doped with neodymium (Nd:YAG) single crystals were grown by the Czochralski technique. Themore » critical diameter and the critical rate of rotation were calculated. Suitable polishing and etching solutions were determined. As a result of our experiments, the transparent YAG and pale pink Nd:YAG single crystals were produced. The obtained crystals were studied by X-ray diffraction, Raman and IR spectroscopy. The crystal structure was confirmed by XRD. The 15 Raman and 17 IR modes were observed. The Raman and IR spectroscopy results are in accordance with X-ray diffraction analysis. The obtained YAG and Nd:YAG single crystals were without core and of good optical quality. The absence of a core was confirmed by viewing polished crystal slices. Also, it is important to emphasize that the obtained Nd:YAG single crystal has a concentration of 0.8 wt.% Nd{sup 3+} that is characteristic for laser materials.« less

Fabrication, characterization and applications of iron selenide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hussain, Raja Azadar, E-mail: hussainazadar@yahoo.com; Badshah, Amin; Lal, Bhajan

This review article presents fabrication of FeSe by solid state reactions, solution chemistry routes, chemical vapor deposition, spray pyrolysis and chemical vapor transport. Different properties and applications such as crystal structure and phase transition, band structure, spectroscopy, superconductivity, photocatalytic activity, electrochemical sensing, and fuel cell activity of FeSe have been discussed. - Graphical abstract: Iron selenide can be synthesized by solid state reactions, chemical vapor deposition, solution chemistry routes, chemical vapor transport and spray pyrolysis. - Highlights: • Different fabrication methods of iron selenide (FeSe) have been reviewed. • Crystal structure, band structure and spectroscopy of FeSe have been discussed.more » • Superconducting, catalytic and fuel cell application of FeSe have been presented.« less

Low-temperature solvothermal synthesis of EuS hollow microspheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Yong; Wang, Hong; Li, Peng

2014-09-15

Graphical abstract: Synthesis of EuS hollow microspheres at low-temperature via solvothermal method for the first time. - Highlights: • We adopt an improved method to synthesise the (Phen)Eu(Et{sub 2}CNS{sub 2}){sub 3} in deionized water. • We have successfully synthesised the EuS hollow microsphere at 230 °C in acetonitrile. • The price of acetonitrile is more inexpensive, so the price of preparation was reduced. - Abstract: EuS crystals are synthesized by low-temperature solvothermal decomposition of the single source precursor complex (Phen)Eu(Et{sub 2}CNS{sub 2}){sub 3} in acetonitrile. X-ray powder diffraction, scanning electron microscopy, granulocyte diameter statistical analysis, surface energy-dispersive X-ray spectroscopy analysis,more » and UV–vis absorption spectroscopy are used to characterize the structure and properties of the obtained EuS crystals. The results show that the formed EuS crystals are uniform hollow microspheres with a typical cubic phase structure of rock salt and the average particle size of 2.01 μm. The mechanisms for the thermal decomposition of the precursor complex and the formation of the EuS hollow microspheres are postulated based on the experimental observations and previous reports.« less

Structure determination and optical properties of CsSm(PO{sub 3}){sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ben Hassen, N.; Ferhi, M., E-mail: ferhi.mounir@gmail.com; Horchani-Naifer, K.

2015-03-15

Graphical abstract: Projection of the CsSm(PO{sub 3}){sub 4} structure viewing along the a axis. - Highlights: • Single crystal of a new polyphosphate CsSm(PO{sub 3}){sub 4} has been synthesized. • The obtained compound has been characterized by several techniques. • The crystal structure of CsSm(PO{sub 3}){sub 4} has been resolved. • Spectroscopic properties of Sm{sup 3+} in CsSm(PO{sub 3}){sub 4} have been performed. - Abstract: A new alkali metal-rare earth polyphosphate CsSm(PO{sub 3}){sub 4} has been synthesized by flux method. The obtained compound has been characterized by means of single crystal X-ray diffraction, Fourier transform infrared (FTIR) and Raman scatteringmore » spectroscopies. It crystallizes in the monoclinic space group P2{sub 1}/n with the following unit-cell parameters: a = 10.382(2), b = 8.978(6), c = 11.205(4) Å, β = 106.398(3)° and Z = 4. The structure of CsSm(PO{sub 3}){sub 4} is an infinite three-dimensional framework made up of double spiral (PO{sub 3}){sub n} chains linked with neighboring SmO{sub 8} and CsO{sub 11} polyhedra. Spectroscopic properties of Sm{sup 3+} in this new compound including excitation, emission, and kinetic measurement have been performed. The emission spectrum shows four transitions characteristics of Sm{sup 3+} in the orange–red region by excitation wavelength at 400 nm. The decay time curve of {sup 4}G{sub 5/2} → {sup 6}H{sub 7/2} transition has been also registered and fitted to a single exponential function.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davaasuren, Bambar; Dashjav, Enkhtsetseg; Kreiner, Guido

The carboferrates RE{sub 15}[Fe{sub 8}C{sub 25}] (RE=Dy, Ho) were prepared from mixtures of the elements by arc-melting followed with subsequent annealing at 1373 K. The crystal structures were determined from single crystal X-ray diffraction data and revealed an isotypic relationship to Er{sub 15}[Fe{sub 8}C{sub 25}] (hP48, P321). The main feature of the crystal structure is given by Fe{sub 6} cluster units characterized by covalent Fe–Fe bonding interactions. {sup 57}Fe Mössbauer spectra of Dy{sub 15}[Fe{sub 8}C{sub 25}] were fitted by three subspectra with relative spectral weights of about 3:3:2 which is in general agreement with the crystal structure. Below 50 K,more » an onset of magnetic hyperfine fields at the three iron sites is observed which is supposed to be caused by dipolar fields arising from neighboring, slowly relaxing Dy magnetic moments. - Graphical abstract: Fe{sub 6}-cluster in the crystal structure of RE{sub 15}[Fe{sub 8}C{sub 25}], RE=Dy, Ho. - Highlights: • New carboferrates RE{sub 15}[Fe{sub 8}C{sub 25}] with RE=Dy, Ho have been synthesized. • The crystal structures were refined using single crystal X-ray data. • An orientational relationship between Fe{sub 6}-clusters and Fe in γ-Fe is outlined. • {sup 57}Fe Mössbauer spectra are in agreement with structural data from X-rays. • Magnetic hyperfine fields below 50 K are explained by dipolar fields from Dy atoms.« less

USSR and Eastern Europe Scientific Abstracts, Physics and Mathematics, Number 39

DTIC Science & Technology

1978-01-17

examination of a monoclinic single crystal has revealed a U022+ iön, and helical polyphosphate chains with six PO4 tetrahedra per link. Corrugated uranyl...mean mass temperature and local Nusselt number. Figures 5; references 13: 3 Russian, 10 Western. USSR UDC 535.334 DETERMINATION OF THE PARAMETERS...Nuclear Research [Abstract] The theory of pion condensation predicts the existence of super- dense nuclei, on the basis of the structure of the

Synthesis and crystal structure analysis of uranyl triple acetates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klepov, Vladislav V., E-mail: vladislavklepov@gmail.com; Department of Chemistry, Samara National Research University, 443086 Samara; Serezhkina, Larisa B.

2016-12-15

Single crystals of triple acetates NaR[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O (R=Mg, Co, Ni, Zn), well-known for their use as reagents for sodium determination, were grown from aqueous solutions and their structural and spectroscopic properties were studied. Crystal structures of the mentioned phases are based upon (Na[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}){sup 2–} clusters and [R(H{sub 2}O){sub 6}]{sup 2+} aqua-complexes. The cooling of a single crystal of NaMg[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O from 300 to 100 K leads to a phase transition from trigonal to monoclinic crystal system. Intermolecular interactions between the structural units and their mutual packing were studiedmore » and compared from the point of view of the stereoatomic model of crystal structures based on Voronoi-Dirichlet tessellation. Using this method we compared the crystal structures of the triple acetates with Na[UO{sub 2}(CH{sub 3}COO){sub 3}] and [R(H{sub 2}O){sub 6}][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} and proposed reasons of triple acetates stability. Infrared and Raman spectra were collected and their bands were assigned. - Graphical abstract: Single crystals of uranium based triple acetates, analytical reagents for sodium determination, were synthesized and structurally, spectroscopically and topologically characterized. The structures were compared with the structures of compounds from preceding families [M(H{sub 2}O){sub 6})][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} (M = Mg, Co, Ni, Zn) and Na[UO{sub 2}(CH{sub 3}COO){sub 3}]. Analysis was performed with the method of molecular Voronoi-Dirichlet polyhedra to reveal a large contribution of the hydrogen bonds into intermolecular interactions which can be a reason of low solubility of studied complexes.« less

Synthesis, characterization, and application of two Al(OR(F))3 Lewis superacids.

PubMed

Kraft, Anne; Trapp, Nils; Himmel, Daniel; Böhrer, Hannes; Schlüter, Peter; Scherer, Harald; Krossing, Ingo

2012-07-23

We report herein the synthesis and full characterization of the donor-free Lewis superacids Al(OR(F))(3) with OR(F) = OC(CF(3))(3) (1) and OC(C(5)F(10))C(6)F(5) (2), the stabilization of 1 as adducts with the very weak Lewis bases PhF, 1,2-F(2)C(6)H(4), and SO(2), as well as the internal C-F activation pathway of 1 leading to Al(2)(F)(OR(F))(5) (4) and trimeric [FAl(OR(F))(2)](3) (5, OR(F) = OC(CF(3))(3)). Insights have been gained from NMR studies, single-crystal structure determinations, and DFT calculations. The usefulness of these Lewis acids for halide abstractions has been demonstrated by reactions with trityl chloride (NMR; crystal structures). The trityl salts allow the introduction of new, heteroleptic weakly coordinating [Cl-Al(OR(F))(3)](-) anions, for example, by hydride or alkyl abstraction reactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Haishuang; Krysiak, Yaşar; Hoffmann, Kristin

The crystal structure and disorder phenomena of Al{sub 4}B{sub 2}O{sub 9}, an aluminum borate from the mullite-type family, were studied using automated diffraction tomography (ADT), a recently established method for collection and analysis of electron diffraction data. Al{sub 4}B{sub 2}O{sub 9}, prepared by sol-gel approach, crystallizes in the monoclinic space group C2/m. The ab initio structure determination based on three-dimensional electron diffraction data from single ordered crystals reveals that edge-connected AlO{sub 6} octahedra expanding along the b axis constitute the backbone. The ordered structure (A) was confirmed by TEM and HAADF-STEM images. Furthermore, disordered crystals with diffuse scattering along themore » b axis are observed. Analysis of the modulation pattern implies a mean superstructure (AAB) with a threefold b axis, where B corresponds to an A layer shifted by ½a and ½c. Diffraction patterns simulated for the AAB sequence including additional stacking disorder are in good agreement with experimental electron diffraction patterns. - Graphical abstract: Crystal structure and disorder phenomena of B-rich Al{sub 4}B{sub 2}O{sub 9} studied by automated electron diffraction tomography (ADT) and described by diffraction simulation using DISCUS. - Highlights: • Ab-initio structure solution by electron diffraction from single nanocrystals. • Detected modulation corresponding mainly to three-fold superstructure. • Diffuse diffraction streaks caused by stacking faults in disordered crystals. • Observed streaks explained by simulated electron diffraction patterns.« less

Synthesis, crystal structure and electronic structure of the binary phase Rh{sub 2}Cd{sub 5}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koley, Biplab; Chatterjee, S.; Jana, Partha P., E-mail: ppj@chem.iitkgp.ernet.in

2017-02-15

A new phase in the Rh-Cd binary system - Rh{sub 2}Cd{sub 5} has been identified and characterized by single crystal X-ray diffraction and Energy dispersive X-ray analysis. The stoichiometric compound Rh{sub 2}Cd{sub 5} crystallizes with a unit cell containing 14 atoms, in the orthorhombic space group Pbam (55). The crystal structure of Rh{sub 2}Cd{sub 5} can be described as a defect form of the In{sub 3}Pd{sub 5} structure with ordered vacancies, formed of two 2D atomic layers with the stacking sequence: ABAB. The A type layers consist of (3.6.3.6)-Kagomé nets of Cd atoms while the B type layers consist ofmore » (3{sup 5}) (3{sup 7})- nets of both Cd and Rh atoms. The stability of this line phase is investigated by first principle electronic structure calculations on the model of ordered Rh{sub 2}Cd{sub 5}. - Graphical abstract: (3.6.3.6)-Kagomé nets of cadmium atoms (top) and (3{sup 5}) (3{sup 7})- nets of both cadmium and rhodium atoms (bottom) in the structure of Rh{sub 2}Cd{sub 5}.« less

Synthesis, structural and optical characterization of APbX{sub 3} (A=methylammonium, dimethylammonium, trimethylammonium; X=I, Br, Cl) hybrid organic-inorganic materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mancini, Alessandro; Quadrelli, Paolo; Amoroso, Giuseppe

2016-08-15

In this paper we report the synthesis, the crystal structure and the optical response of APbX{sub 3} (A=MA, DMA, and TMA; X=I, Br) hybrid organic-inorganic materials including some new phases. We observe that as the cation group increases in size, the optical absorption edge shifts to higher energies with energy steps which are systematic and independent on the anion. A linear correlation between the optical bad gap and the tolerance factor has been shown for the series of samples investigated. - Graphical abstract: The crystal structure and the optical response of the two series of hybrid organic-inorganic materials APbX{sub 3}more » (A=MA, DMA, and TMA; X=I, Br), which include some new phases, are reported. A dependence of crystal structure and band-gap with tolerance factor is shown. Display Omitted - Highlights: • DMAPbI{sub 3}, TMAPbI{sub 3} and TMAPbBr{sub 3} are reported as new hybrid organic-inorganic compounds. • Crystal structure and optical properties as a function of the number of methyl groups are provided. • Correlation between structure and optical properties are given as a function of tolerance factor.« less

Synthesis, crystal structure, and magnetic properties of two-dimensional divalent metal glutarate/dipyridylamine coordination polymers, with a single crystal-to-single crystal transformation in the copper derivative

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montney, Matthew R.; Supkowski, Ronald M.; Staples, Richard J.

Hydrothermal reaction of divalent metal chlorides with glutaric acid and 4,4'-dipyridylamine (dpa) has afforded an isostructural family of coordination polymers with formulation [M(glu)(dpa)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate). Square pyramidal coordination is seen in 1-3, with semi-ligation of a sixth donor to produce a '5+1' extended coordination sphere. Neighboring metal atoms are linked into 1D [M(glu)]{sub n} neutral chains through chelating/monodentate bridging glutarate moieties with a syn-anti binding mode, and semi-chelation of the pendant carboxylate oxygen. These chains further connect into 2D layers through dipodal dpa ligands. Neighboring layers stack into the pseudo 3D crystal structure ofmore » 1-3 through supramolecular hydrogen bonding between dpa amine units and the semi-chelated glutarate oxygen atoms. The variable temperature magnetic behavior of 1-3 was explored and modeled as infinite 1D Heisenberg chains. Notably, complex 3 undergoes a thermally induced single crystal-to-single crystal transformation between centric and acentric space groups, with a conformationally disordered unilayer structure at 293 K and an ordered bilayer structure at 173 K. All materials were further characterized via infrared spectroscopy and elemental and thermogravimetric analyses. - Graphical abstract: The coordination polymers [M(glu)(dpa)]{sub n} (M=Co (1), Ni (2), Cu (3); glu=glutarate, dpa=4,4'-dipyridylamine) exhibit 2D layer structures based on 1D [M(glu)]{sub n} chains linked through dpa tethers. Antiferromagnetic coupling is observed for 2 and 3, while ferromagnetism is predominant in 1. Compound 3 undergoes a thermally induced single crystal-to-single crystal transformation from an acentric to a centrosymmetric space group.« less

From Two‐ to Three‐Dimensional Structures of a Supertetrahedral Boran Using Density Functional Calculations

PubMed Central

Getmanskii, Iliya V.; Steglenko, Dmitrii V.; Koval, Vitaliy V.; Zaitsev, Stanislav A.

2017-01-01

Abstract With help of the DFT calculations and imposing of periodic boundary conditions the geometrical and electronic structures were investigated of two‐ and three‐dimensional boron systems designed on the basis of graphane and diamond lattices in which carbons were replaced with boron tetrahedrons. The consequent studies of two‐ and three‐layer systems resulted in the construction of a three‐dimensional supertetrahedral borane crystal structure. The two‐dimensional supertetrahedral borane structures with less than seven layers are dynamically unstable. At the same time the three‐dimensional superborane systems were found to be dynamically stable. Lack of the forbidden electronic zone for the studied boron systems testifies that these structures can behave as good conductors. The low density of the supertetrahedral borane crystal structures (0.9 g cm−3) is close to that of water, which offers the perspective for their application as aerospace and cosmic materials. PMID:28402596

Controlled synthesis of BiVO{sub 4} with multiple morphologies via an ethylenediamine-assisted hydrothermal method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qi, Xuemei, E-mail: qixuemei@shiep.edu.cn; School of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090; Zhu, Xinyuan

2014-11-15

Graphical abstract: BiVO{sub 4} samples with various morphologies were synthesized via a simple ethylenediamine (EN) assisted hydrothermal route. One of the mixed crystal phase with spherical and porous morphology showed excellent photocatalytic activity and about 90% Rhodamine B was degraded after 140 min visible light irradiation. - Highlights: • BiVO{sub 4} samples with various morphologies were synthesized by hydrothermal method. • Ethylenediamine mainly acts as alkaline source to adjust pH values of precursor. • BiVO{sub 4} with spherical morphology has excellent photocatalytic activity. - Abstract: In this work, BiVO{sub 4} particles with different crystal structures and morphologies including hexahedral, sphericalmore » porous and hyperbranched ones were fabricated in the presence of ethylenediamine by hydrothermal process. The as-fabricated samples were well characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and ultraviolet–visible absorption spectroscopy. The results showed that the morphology and crystal structure of BiVO{sub 4} particles could be well controlled by only changing the ethylenediamine content in the deionized water solution. Photocatalytic activity of the samples was evaluated by the degradation of Rhodamine B under visible-light irradiation. It was shown that BiVO{sub 4} sample with spherical porous morphology and mixed crystal phase exhibited the best photocatalytic performance after optimizing the ethylenediamine content. The best degradation ratio of Rhodamine B could reach about 87% after 140 min visible-light irradiation.« less

Preparation and electrocatalytic activity of tungsten carbide and titania nanocomposite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Sujuan; Shi, Binbin; Yao, Guoxing

2011-10-15

Graphical abstract: The electrocatalytic activity of tungsten carbide and titania nanocomposite is related to the structure, crystal phase and chemical components of the nanocomposite, and is also affected by the property of electrolyte. A synergistic effect exists between tungsten carbide and titania of the composite. Highlights: {yields} Electrocatalytic activity of tungsten carbide and titania nanocomposite with core-shell structure. {yields} Activity is related to the structure, crystal phase and chemical component of the nanocomposite. {yields} The property of electrolyte affects the electrocatalytic activity. {yields} A synergistic effect exists between tungsten carbide and titania of the composite. -- Abstract: Tungsten carbide andmore » titania nanocomposite was prepared by combining a reduced-carbonized approach with a mechanochemical approach. The samples were characterized by X-ray diffraction, transmission electron microscope under scanning mode and X-ray energy dispersion spectrum. The results show that the crystal phases of the samples are composed of anatase, rutile, nonstoichiometry titanium oxide, monotungsten carbide, bitungsten carbide and nonstoichiometry tungsten carbide, and they can be controlled by adjusting the parameters of the reduced-carbonized approach; tungsten carbide particles decorate on the surface of titania support, the diameter of tungsten carbide particle is smaller than 20 nm and that of titania is around 100 nm; the chemical components of the samples are Ti, O, W and C. The electrocatalytic activity of the samples was measured by a cyclic voltammetry with three electrodes. The results indicate that the electrocatalytic activities of the samples are related to their crystal phases and the property of electrolyte in aqueous solution. A synergistic effect between titania and tungsten carbide is reported for the first time.« less

ICCG-10: Tenth International Conference on Crystal Growth. Oral presentation abstracts

NASA Technical Reports Server (NTRS)

1992-01-01

Oral presentation abstracts from the tenth International Conference on Crystal Growth (ICCG) (Aug. 16-21, 1992) are provided. Topics discussed at the conference include superconductors, semiconductors, nucleation, crystal growth mechanisms, and laser materials. Organizing committees, ICCG advisory board and officers, and sponsors of the conference are also included.

Growth, structural, optical, thermal and mechanical properties of cytosinium hydrogen selenite: A novel nonlinear optical single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaikumar, P.; Sathiskumar, S.; Balakrishnan, T., E-mail: balacrystalgrowth@gmail.com

Highlights: • Growth of bulk single crystals of cytosinium hydrogen selenite (CHS) is reported. • Dielectric constant of CHS is measured as a function of Frequency and temperature. • Lower cut off value of UV–vis-NIR spectrum of CHS crystal is observed at 210 nm. • Meyer’s index value of CHS crystal calculated identifies it as a soft material. • Powder SHG efficiency of CHS is about 1.5 times that of KDP crystal. - Abstract: A novel nonlinear optical single crystal of cytosinium hydrogen selenite was grown from aqueous solution of cytosinium hydrogen selenite by slow solvent evaporation method at roommore » temperature. The structural properties of grown crystal have been studied by single crystal and powder X-ray diffraction analysis. Presence of various functional groups was identified from Fourier transform infrared spectroscopy. The optical transmittance and absorbance spectra were recorded by UV–vis-NIR spectrometer and the grown crystal possesses good transparency in the entire visible region. The dielectric constant and dielectric loss of the crystal were calculated as a function of frequency at different temperatures. The mechanical strength of the cytosinium hydrogen selenite crystal was estimated using Vicker’s microhardness tester. Etch patterns of the cytosinium hydrogen selenite crystal were obtained using distilled water as etchant for different etching time. Second harmonic generation efficiency tested using Nd:YAG laser is about 1.5 times that of KDP.« less

Crystal structure of glycoside hydrolase family 127 β-L-arabinofuranosidase from Bifidobacterium longum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ito, Tasuku; Saikawa, Kyo; Kim, Seonah

2014-04-25

Graphical abstract: - Highlights: • HypBA1 β-L-arabinofuranosidase belongs to glycoside hydrolase family 127. • Crystal structure of HypBA1 was determined. • HypBA1 consists of a catalytic barrel and two additional β-sandwich domains. • The active site contains a Zn{sup 2+} coordinated by glutamate and three cysteines. • A possible reaction mechanism involving cysteine as the nucleophile is proposed. - Abstract: Enzymes acting on β-linked arabinofuranosides have been unknown until recently, in spite of wide distribution of β-L-arabinofuranosyl oligosaccharides in plant cells. Recently, a β-L-arabinofuranosidase from the glycoside hydrolase family 127 (HypBA1) was discovered in the newly characterized degradation system ofmore » hydroxyproline-linked β-L-arabinooligosaccharides in the bacterium Bifidobacterium longum. Here, we report the crystal structure of HypBA1 in the ligand-free and β-L-arabinofuranose complex forms. The structure of HypBA1 consists of a catalytic barrel domain and two additional β-sandwich domains, with one β-sandwich domain involved in the formation of a dimer. Interestingly, there is an unprecedented metal-binding motif with Zn{sup 2+} coordinated by glutamate and three cysteines in the active site. The glutamate residue is located far from the anomeric carbon of the β-L-arabinofuranose ligand, but one cysteine residue is appropriately located for nucleophilic attack for glycosidic bond cleavage. The residues around the active site are highly conserved among GH127 members. Based on biochemical experiments and quantum mechanical calculations, a possible reaction mechanism involving cysteine as the nucleophile is proposed.« less

Communication: Hot-atom abstraction dynamics of hydrogen from tungsten surfaces: The role of surface structure

NASA Astrophysics Data System (ADS)

Galparsoro, Oihana; Busnengo, Heriberto Fabio; Juaristi, Joseba Iñaki; Crespos, Cédric; Alducin, Maite; Larregaray, Pascal

2017-09-01

Adiabatic and non-adiabatic quasiclassical molecular dynamics simulations are performed to investigate the role of the crystal face on hot-atom abstraction of H adsorbates by H scattering from covered W(100) and W(110). On both cases, hyperthermal diffusion is strongly affected by the energy dissipated into electron-hole pair excitations. As a result, the hot-atom abstraction is highly reduced in favor of adsorption at low incidence energy and low coverages, i.e., when the mean free path of the hyperthermal H is typically larger. Qualitatively, this reduction is rather similar on both surfaces, despite at such initial conditions, the abstraction process involves more subsurface penetration on W(100) than on W(110).

Rapid crystallization and morphological adjustment of zeolite ZSM-5 in nonionic emulsions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Ying, E-mail: yingzh1977@163.co; Jin Chao; Research Institute of Petroleum Processing, Beijing 100083

2011-01-15

Zeolite ZSM-5 was synthesized for the first time in a nonionic emulsion composed of polyoxyethylated alkylphenol, butanol, cyclohexane and tetraethylammonium hydroxide (TEAOH)-containing zeolite synthesis mixture. The crystallization kinetics in the emulsion was investigated and the ZSM-5 product was characterized in detail by XRD, SEM, FT-IR, TG, N{sub 2} adsorption and CHN analysis techniques. Compared with the conventionally hydrothermal synthesis with the same structure directing agent TEAOH, the emulsion system allows rapid crystallization of ZSM-5. The ZSM-5 product exhibits unusual agglomerated structure and possesses larger specific surface area. The FT-IR, TG results plus CHN analysis show the encapsulation of a tracemore » of emulsion components in the emulsion ZSM-5. Control experiments show the emulsion system exerts the crystallization induction and morphological adjustment effects mainly during the aging period. The effects are tentatively attributed to the confined space domains, surfactant-water interaction as well as surfactant-growing crystals interaction existing in the emulsion. -- Graphical abstract: The nonionic emulsion synthesis allows rapid crystallization and morphological adjustment of zeolite ZSM-5 compared with the conventional hydrothermal synthesis. Display Omitted« less

Crystal structure, optical and thermal studies of a new organic nonlinear optical material: L-Histidinium maleate 1.5-hydrate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gonsago, C. Alosious; Albert, Helen Merina; Karthikeyan, J.

2012-07-15

Highlights: ► L-Histidinium maleate 1.5-hydrate, a new organic crystal has been grown for the first time. ► The crystal structure is reported for the first time (CCDC 845975). ► The crystal belongs to monoclinic system with space group P2{sub 1}, Z = 4, a = 11.4656(7) Å, b = 8.0530(5) Å, c = 14.9705(9) Å and β = 101.657(2)°. ► The optical absorption study substantiates the complete transparency of the crystal. ► Kurtz powder SHG test confirms the nonlinear property of the crystal. -- Abstract: A new organic nonlinear optical material L-histidinium maleate 1.5-hydrate (LHM) with the molecular formula C{submore » 10}H{sub 16}N{sub 3}O{sub 7.5} has been successfully synthesized from aqueous solution by slow solvent evaporation method. The structural characterization of the grown crystal was carried out by single crystal X-ray diffraction at 293(2) K. In the crystal, molecules are linked through inter and intramolecular N-H⋯O and O-H⋯O hydrogen bonds, generate edge fused ring motif. The hydrogen bonded motifs are linked to each other to form a three dimensional network. The FT-IR spectroscopy was used to identify the functional groups of the synthesized compound. The optical behavior of the grown crystal was examined by UV–visible spectral analysis, which shows that the optical absorption is almost negligible in the wavelength range 280–1300 nm. The nonlinear optical property was confirmed by the powder technique of Kurtz and Perry. The thermal behavior of the grown crystal was analyzed by thermogravimetric analysis.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ben Yahia, Hamdi, E-mail: benyahia.hamdi@voila.fr; Rodewald, Ute Ch.; Boulahya, Khalid

Graphical abstract: The new compounds RE{sub 4}O{sub 4}[AsO{sub 4}]Cl (RE = La, Pr, Nd, Sm, Eu, Gd) were synthesised by solid state reaction via a salt flux route and investigated by HRTEM, SAED, and single crystal X-ray diffraction. - Highlights: • We discovered the series of RE{sub 4}O{sub 4}[AsO{sub 4}]Cl (RE = La, Pr, Nd, Sm, Eu, Gd) compounds. • The RE{sub 4}O{sub 4}[AsO{sub 4}]Cl single crystals were grown using NaCl/KCl flux. • The RE{sub 4}O{sub 4}[AsO{sub 4}]Cl structures were solved using single crystal X-ray diffraction data. • The layered RE{sub 4}O{sub 4}[AsO{sub 4}]Cl compounds were further characterized using HRTEMmore » and SAED. • We observed an alternation of ordered-[RE{sub 4}O{sub 4}]{sup 4+} and disordered-[ClAsO{sub 4}]{sup 4–} layers. - Abstract: The new compounds RE{sub 4}O{sub 4}[AsO{sub 4}]Cl (RE = La, Pr, Nd, Sm, Eu, Gd) were synthesised by solid state reaction via a salt flux route and investigated by HRTEM, SAED, and single crystal X-ray diffraction. The samples crystallise with a tetragonal cell, space group P4{sub 2}/mnm and Z = 2. Their crystal structure consists of an alternation of [RE{sub 4}O{sub 4}]{sup 4+} and [ClAsO{sub 4}]{sup 4–} layers. The [RE{sub 4}O{sub 4}]{sup 4+} layer contains ORE{sub 4/4} tetrahedra which share common edges. The anions AsO{sub 4}{sup 3–} and Cl{sup –} are located between these layers in disordered manner. SAED and HRTEM experiments confirmed this structural model and enabled us to propose an ordered model for the [ClAsO{sub 4}]{sup 4–} layers.« less

Hydrothermal synthesis for new multifunctional materials: A few examples of phosphates and phosphonate-based hybrid materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rueff, Jean-Michel, E-mail: jean-michel.rueff@ensicaen.fr; Poienar, Maria; Guesdon, Anne

Novel physical or chemical properties are expected in a great variety of materials, in connection with the dimensionality of their structures and/or with their nanostructures, hierarchical superstructures etc. In the search of new advanced materials, the hydrothermal technique plays a crucial role, mimicking the nature able to produce fractal, hyperbranched, urchin-like or snow flake structures. In this short review including new results, this will be illustrated by examples selected in two types of materials, phosphates and phosphonates, prepared by this method. The importance of the synthesis parameters will be highlighted for a magnetic iron based phosphates and for hybrids containingmore » phosphonates organic building units crystallizing in different structural types. - Graphical abstract: Phosphate dendrite like and phosphonate platelet crystals.« less

Crystal growth and electronic structure of low-temperature phase SrMgF{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atuchin, Victor V.; Functional Electronics Laboratory, Tomsk State University, Tomsk 634050; Laboratory of Semiconductor and Dielectric Materials, Novosibirsk State University, Novosibirsk 630090

2016-04-15

Using the vertical Bridgman method, the single crystal of low temperature phase SrMgF{sub 4} is obtained. The crystal is in a very good optical quality with the size of 10×7×5 mm{sup 3}. Detailed photoemission spectra of the element core levels are determined by a monochromatic AlKa (1486.6 eV) X-ray source. Moreover, the first-principles calculations are performed to investigate the electronic structure of SrMgF{sub 4}. A good agreement between experimental and calculated results is achieved. It is demonstrated that almost all the electronic orbitals are strongly localized and the hybridization with the others is very small, but the Mg–F bonds covalencymore » is relatively stronger than that of Sr–F bonds. - Graphical abstract: Large size of low-temperature phase SrMgF{sub 4} crystal was obtained (right) and its electronic structure was investigated by X-ray photoelectron spectroscopy and first-principles calculation (left). - Highlights: • Large size single crystal of low-temperature phase SrMgF{sub 4} is obtained. • Electronic structure of SrMgF{sub 4} is measured by X-ray photoelectron spectroscopy. • Partial densities of states are determined by first-principles calculation. • Good agreement between experimental and calculated results is achieved. • Strong ionic characteristics of chemical bonds are exhibited in SrMgF{sub 4}.« less

ICCG-10: Tenth International Conference on Crystal Growth. Poster presentation abstracts

NASA Technical Reports Server (NTRS)

1992-01-01

Poster presentation abstracts from the tenth International Conference on Crystal Growth (ICCG) (Aug. 16-21, 1992) are provided. Topics discussed at the conference include crystal growth mechanisms, superconductors, semiconductors, laser materials, optical materials, and biomaterials. Organizing committees, ICCG advisory board and officers, and sponsors of the conference are also included.

Crystal structure, electronic structure, and photoluminescent properties of SrMoO{sub 4}:Tb{sup 3+} phosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Sung Wook; Moon, Byung Kee; Jeong, Jung Hyun, E-mail: jhjeong@pknu.ac.kr

2015-10-15

Highlights: • SrMoO{sub 4}:Tb{sup 3+} phosphor samples were synthesized at different temperatures. • The crystal and electronic structures, and luminescence properties were studied. • The excitation peak shifts to red with increasing the sintering temperature. • The luminescence mechanism of SrMoO{sub 4}:Tb{sup 3+} was suggested. - Abstract: The experimental and theoretical studies of the optical properties of SrMoO{sub 4}:Tb{sup 3+} phosphors were carried out. The structural, optical, and electronical properties of the phosphors were systematically studied. The phosphor samples were crystallized at different temperatures via a sol–gel method. Excitation spectra of SrMoO{sub 4}:Tb{sup 3+} powder samples exhibited gradual red shiftmore » and luminescent intensity changed with increasing the sintering temperature. Such spectral changes depend strongly on the crystallographic properties such as lattice parameters and crystallinity. The shift of the excitation spectra is mainly ascribed to the covalent bond interaction between Mo−O bonds. An energy band model was demonstrated to describe the luminescence mechanism in the material.« less

A novel fabrication of Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell micro/nanocrystals from Cu{sub 2}O temples and enhanced photocatalytic activities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Junqi, E-mail: sfmlab@163.com; Sun, Long; Yan, Ying

2016-08-15

Highlights: • The Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell crystals maintained the same morphology with template. • The crystals exhibit enhanced photocatalytic activity than the pure Cu{sub 2}O crystals. • The photocatalytic activity of different R crystals is diverse from each other. • A possible formation mechanism has been proposed. - Abstract: Uniform and monodispersed Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell micro/nanocrystals have been synthesized successfully at room temperature via a simple chemical etching reaction, using Cu{sub 2}O as sacrificial template. The structure and properties of the crystals were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM),more » X-ray photoelectron spectra (XPS). The photocatalytic activity of the Cu{sub 2}O@Cu{sub 7}S{sub 4} crystals was evaluated by photocatalytic decolorization of MeO (methyl orange) aqueous solution at ambient temperature under visible-light irradiation. The results show that the as-prepared Cu{sub 2}O@Cu{sub 7}S{sub 4} crystals revealed core-shell structure, which maintained the same morphology with corresponding template and were composed of cuboctahedron Cu{sub 7}S{sub 4} shell and active Cu{sub 2}O core. Due to the unique Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell structure, the crystals exhibit enhanced photocatalytic activity than that of the pure Cu{sub 2}O crystals, and the photocatalytic activity of different R crystals is diverse from each other. A possible formation mechanism has been proposed.« less

Nineteenth Lunar and Planetary Science Conference. Press abstracts

NASA Technical Reports Server (NTRS)

1988-01-01

Topics addressed include: origin of the moon; mineralogy of rocks; CO2 well gases; ureilites; antarctic meteorites; Al-26 decay in a Semarkona chondrule; meteorite impacts on early earth; crystal structure and density of helium; Murchison carbonaceous chondrite composition; greenhouse effect and dinosaurs; Simud-Tiu outflow system of Mars; and lunar radar images.

Nineteenth lunar and planetary science conference. Press abstracts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1988-01-01

Topics addressed include: origin of the moon; mineralogy of rocks; CO2 well gases; ureilites; antarctic meteorites; Al-26 decay in a Semarkona chondrule; meteorite impacts on early earth; crystal structure and density of helium; Murchison carbonaceous chondrite composition; greenhouse effect and dinosaurs; Simud-Tiu outflow system of Mars; and lunar radar images.

A novel organic–inorganic hybrid with Anderson type polyanions as building blocks: (C{sub 6}H{sub 10}N{sub 3}O{sub 2}){sub 2}Na(H{sub 2}O){sub 2}[Al(OH){sub 6}Mo{sub 6}O{sub 18}]·6H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thabet, Safa, E-mail: safathabet@hotmail.fr; Ayed, Brahim, E-mail: brahimayed@yahoo.fr; Haddad, Amor

Graphical abstract: Display Omitted Highlights: ► Synthesis of a novel inorganic–organic hybrid compound based on Anderson polyoxomolybdates. ► Characterization by X-ray diffraction, IR and UV–Vis spectroscopies of the new compound. ► Potential applications in catalysis, biochemical analysis and electrical conductivity of the organic–inorganic compound. -- Abstract: A new organic–inorganic hybrid compound based on Anderson polyoxomolybdates, (C{sub 6}H{sub 10}N{sub 3}O{sub 2}){sub 2}Na(H{sub 2}O){sub 2}[Al(OH){sub 6}Mo{sub 6}O{sub 18}]·6H{sub 2}O (1) have been isolated by the conventional solution method and characterized by single-crystal X-ray diffraction, infrared, ultraviolet spectroscopy and Thermogravimetric Analysis (TGA). This compound crystallized in the triclinic system, space group P−1, withmore » a = 94.635(1) Å, b = 10.958(1) Å, c = 11.602(1) Å, α = 67.525(1)°, β = 71.049(1)°, γ = 70.124(1)° and Z = 1. The crystal structures of the compounds exhibit three-dimensional supramolecular assembly based on the extensive hydrogen bonding interactions between organic cations, sodium cations, water molecules and Anderson polyoxoanions. The infrared spectrum fully confirms the X-ray crystal structure and the UV spectrum of the title compound exhibits an absorption peak at 210 nm.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Xiaomei; Lv, Xin; Wang, Limin

Graphical abstract: - Highlights: • Effect of CTAB on the morphology and crystallization of MnFe{sub 2}O{sub 4}. • The lowest coercivity of MnFe{sub 2}O{sub 4} polyhedron is 11.9 Oe. • MnFe{sub 2}O{sub 4} as anode for LIB shows good reversible capacity and cycle performances. - Abstract: The uniform different morphologies MnFe{sub 2}O{sub 4}, including cube, truncated cube, polyhedron and octahedron, were successfully synthesized via a solvothermal route using cetyltrimethylammonium bromide. The results of control experiments revealed that the concentration of cetyltrimethylammonium bromide was an important factor, which affected the morphology and crystallization of MnFe{sub 2}O{sub 4} submicro-crystals. All the preparedmore » samples exhibited soft-magnetic behavior at room temperature. Especially, the coercivity of MnFe{sub 2}O{sub 4} polyhedron with 200 nm diameter was 11.9 Oe, which was among the lowest values reported so far. Moreover, MnFe{sub 2}O{sub 4} submicro-crystals with special morphologies demonstrated higher reversible capacity (about 1000 mAh g{sup −1}) and different cycle performances. After 50 cycles, polyhedron structure remained 428 mAh/g. The MnFe{sub 2}O{sub 4} would have a potential application as anode material for lithium ion batteries.« less

A new route for the synthesis of titanium silicalite-1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasile, Aurelia, E-mail: aurelia_vasile@yahoo.com; Busuioc-Tomoiaga, Alina Maria; Catalysis Research Department, ChemPerformance SRL, Iasi 700337

2012-01-15

Graphical abstract: Well-prepared TS-1 was synthesized by an innovative procedure using inexpensive reagents such as fumed silica and TPABr as structure-directing agent. This is the first time when highly crystalline TS-1 is obtained in basic medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source has been prevented by titanium complexation with acetylacetone before structuring gel. Highlights: Black-Right-Pointing-Pointer TS-1 was obtained using cheap reagents as fumed silica and tetrapropylammonium bromide. Black-Right-Pointing-Pointer First time NaOH was used as source of OH{sup -} ions required for crystallization process. Black-Right-Pointing-Pointer The hydrolysis Ti alkoxides wasmore » controlled by Ti complexation with 2,4-pentanedione. -- Abstract: A new and efficient route using inexpensive reagents such as fumed silica and tetrapropylammonium bromide is proposed for the synthesis of titanium silicalite-1. High crystalline titanium silicalite-1 was obtained in alkaline medium, using sodium hydroxide as HO{sup -} ion source required for the crystallization process. Hydrolysis of titanium source with formation of insoluble oxide species was prevented by titanium complexation with before structuring gel. The final solids were fully characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared, ultraviolet-visible diffuse reflectance, Raman and atomic absorption spectroscopies, as well as nitrogen sorption analysis. It was found that a molar ratio Ti:Si of about 0.04 in the initial reaction mixture is the upper limit to which well formed titanium silicalite-1 with channels free of crystalline or amorphous material can be obtained. Above this value, solids with MFI type structure containing both Ti isomorphously substituted in the network and extralattice anatase nanoparticles inside of channels is formed.« less

Synthesis, crystal structure, and electrical and magnetic properties of BaMo{sub 6}Te{sub 6}: A novel reduced molybdenum telluride containing infinite chains of trans-face shared Mo{sub 6} octahedra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gall, Philippe; Guizouarn, Thierry; Potel, Michel

Powder samples and single crystals of the new ternary compound BaMo{sub 6}Te{sub 6} were obtained by solid state reaction. The structure was determined by single-crystal X-ray diffraction. BaMo{sub 6}Te{sub 6} crystallizes in the hexagonal space group P6{sub 3}/m (No. 176) with unit-cell parameters a=9.3941(2) Å, c=4.5848(1) Å and Z=1. Full-matrix least-squares refinement on F{sup 2} using 452 independent reflections for 17 refinable parameters resulted in R1=0.0208 and wR2=0.0539. The structure consists of one-dimensional infinite chains of trans-face shared Mo{sub 6} octahedra capped by Se atoms. These chains that are running along the c axis are separated from each other bymore » nine-coordinate Ba atoms. Resistivity measurements on a single crystal indicated that the BaMo{sub 6}Te{sub 6} compound is metallic down to 160 K and semiconductor below. Magnetic susceptibility measurements showed that BaMo{sub 6}Te{sub 6} is weakly diamagnetic with no anomaly at the metal–semiconductor transition. - Graphical abstract: We present here the synthesis, the crystal structure, and the electrical and magnetic properties of the new compound BaMo{sub 6}Te{sub 6} containing infinite chains of trans-face shared Mo{sub 6} octahedra. - Highlights: • BaMo{sub 6}Te{sub 6} contains infinite chains of trans-face-sharing Mo{sub 6} octahedra |Mo{sub 6/2}|{sub ∞}{sup 1}. • Synthesis by solid state reaction. • Single-crystal X-ray study. • Continuous metal–nonmetal transition. • Anderson localization.« less

High-resolution three-dimensional imaging of red blood cells parasitized by Plasmodium falciparum and in situ hemozoin crystals using optical diffraction tomography

PubMed Central

Kim, Kyoohyun; Yoon, HyeOk; Diez-Silva, Monica; Dao, Ming; Dasari, Ramachandra R.

2013-01-01

Abstract. We present high-resolution optical tomographic images of human red blood cells (RBC) parasitized by malaria-inducing Plasmodium falciparum (Pf)-RBCs. Three-dimensional (3-D) refractive index (RI) tomograms are reconstructed by recourse to a diffraction algorithm from multiple two-dimensional holograms with various angles of illumination. These 3-D RI tomograms of Pf-RBCs show cellular and subcellular structures of host RBCs and invaded parasites in fine detail. Full asexual intraerythrocytic stages of parasite maturation (ring to trophozoite to schizont stages) are then systematically investigated using optical diffraction tomography algorithms. These analyses provide quantitative information on the structural and chemical characteristics of individual host Pf-RBCs, parasitophorous vacuole, and cytoplasm. The in situ structural evolution and chemical characteristics of subcellular hemozoin crystals are also elucidated. PMID:23797986

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ben Smida, Youssef; Marzouki, Riadh; Georges, Samuel

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, andmore » its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.« less

VO{sub 2} (A): Reinvestigation of crystal structure, phase transition and crystal growth mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao Popuri, Srinivasa; University of Bordeaux, ICMCB, UPR 9048, F-33608 Pessac; National Institute for Research and Development in Electrochemistry and Condensed Matter, Timisoara, Plautius Andronescu Str. No. 1, 300224 Timisoara

2014-05-01

Well crystallized VO{sub 2} (A) microrods were grown via a single step hydrothermal reaction in the presence of V{sub 2}O{sub 5} and oxalic acid. With the advantage of high crystalline samples, we propose P4/ncc as an appropriate space group at room temperature. From morphological studies, we found that the oriented attachment and layer by layer growth mechanisms are responsible for the formation of VO{sub 2} (A) micro rods. The structural and electronic transitions in VO{sub 2} (A) are strongly first order in nature, and a marked difference between the structural transition temperatures and electronic transitions temperature was evidenced. The reversiblemore » intra- (LTP-A to HTP-A) and irreversible inter- (HTP-A to VO{sub 2} (M1)) structural phase transformations were studied by in-situ powder X-ray diffraction. Attempts to increase the size of the VO{sub 2} (A) microrods are presented and the possible formation steps for the flower-like morphologies of VO{sub 2} (M1) are described. - Graphical abstract: Using a single step and template free hydrothermal synthesis, well crystallized VO{sub 2} (A) microrods were prepared and the P4/ncc space group was assigned to the room temperature crystal structure. Reversible and irreversible phase transitions among different VO{sub 2} polymorphs were identified and their progressive nature was highlighted. Attempts to increase the microrods size, involving layer by layer formation mechanisms, are presented. - Highlights: • Highly crystallized VO{sub 2} (A) microrods were grown via a single step hydrothermal process. • The P4/ncc space group was determined for VO{sub 2} (A) at room temperature. • The electronic structure and progressive nature of the structural phase transition were investigated. • A weak coupling between structural and electronic phase transitions was identified. • Different crystallite morphologies were discussed in relation with growth mechanisms.« less

Crystal structure of cocosin, a potential food allergen from coconut (Cocos nucifera) (abstract)

USDA-ARS?s Scientific Manuscript database

RATIONALE: Coconut allergy cases have been reported, but only one coconut allergen has been identified. The 11S seed storage proteins belong to one of a few protein families that contain known food allergens in many food of plant sources. Cocosin, the 11S protein from cocosin remains to be character...

Second All-Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Abstracts of reports: Table of contents

NASA Technical Reports Server (NTRS)

Gershuni, G. Z.; Zhukhovitskiy, Y. M.

1984-01-01

Abstracts of reports are given which were presented at the Second All Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Topics inlcude: (1) features of crystallization of semiconductor materials under conditions of microacceleration; (2) experimental results of crystallization of solid solutions of CDTE-HGTE under conditions of weightlessness; (3) impurities in crystals cultivated under conditions of weightlessness; and (4) a numerical investigation of the distribution of impurities during guided crystallization of a melt.

Effects of scandium substitution on the crystal structure and luminescence properties of LuBO{sub 3}: Ce{sup 3+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yuntao, E-mail: caswyt@hotmail.com; Ren, Guohao, E-mail: rgh@mail.sic.ac.cn; Ding, Dongzhou

2012-10-15

The calcite phase of LuBO{sub 3} and ScBO{sub 3} polycrystalline powders were synthesized by solid state reaction method, and the Lu{sub 1-x}Sc{sub x}BO{sub 3}:Ce (x=0.2, 0.5, 0.7) single crystals were grown by the Czochralski method. A large composition deviation between the initial polycrystalline powders and final single crystal was confirmed by electron probe micro-analysis. Raman spectroscopy revealed that moderate lattice disorder was induced by scandium substitution. However, based on the single crystal X-ray study, we finally concluded that the crystal structure of lutetium scandium orthoborate still crystallized in the rhombohedral system belonging to R3{sup -}c. Furthermore, the relationship between themore » energies of the five 5d levels of Ce{sup 3+} and the crystalline environment was revealed. The total redshift, total crystal field splitting, and centroid shift of Lu{sub 1-x}Sc{sub x}BO{sub 3}:Ce{sup 3+} were calculated based on their VUV excitation spectra. The variations trend of these observed spectroscopic parameters was in accordance with the predicted ones. - Graphical abstract: The crystal structure of Lu{sub 1-x}Sc{sub x}BO{sub 3}:Ce is rhombohedral system with R3{sup -}c space group. The relationship between the energies of the five Ce{sup 3+} 5d levels and the crystalline environment is established. Highlights: Black-Right-Pointing-Pointer Moderate lattice disorder is induced by scandium doping. Black-Right-Pointing-Pointer The crystal structure of Lu{sub 1-x}Sc{sub x}BO{sub 3}:Ce is rhombohedral system with R3{sup -}c space group. Black-Right-Pointing-Pointer Relationship between energies of Ce{sup 3+} 5d levels and crystalline environment is established. Black-Right-Pointing-Pointer The spectroscopic parameters are experimentally and theoretically calculated.« less

Synthesis, structure, and polymorphism of A{sub 3}LnSi{sub 2}O{sub 7} (A=Na, K; Ln=Sm, Ho, Yb)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latshaw, Allison M.; Yeon, Jeongho; Smith, Mark D.

2016-03-15

Four new members of the A{sub 3}LnSi{sub 2}O{sub 7} family, K{sub 3}SmSi{sub 2}O{sub 7}, Na{sub 3}HoSi{sub 2}O{sub 7}, and two polymorphs of Na{sub 3}YbSi{sub 2}O{sub 7}, are reported. K{sub 3}SmSi{sub 2}O{sub 7} crystallizes in the hexagonal space group P6{sub 3}/mcm, Na{sub 3}HoSi{sub 2}O{sub 7} and Na{sub 3}YbSi{sub 2}O{sub 7} crystallize in the hexagonal space group P6{sub 3}/m, and Na{sub 3}YbSi{sub 2}O{sub 7} crystallizes in the trigonal space group P31c. The Na{sub 3}YbSi{sub 2}O{sub 7} composition that crystallizes in P31c is a new structure type. The magnetic properties for the Ho and Yb analogs are reported. - Graphical abstract: The differentmore » structure types and polymorphs of the A{sub 3}LnSi{sub 2}O{sub 7} family reported. - Highlights: • Four new members of the A{sub 3}LnSi{sub 2}O{sub 7} family are presented. • Na{sub 3}YbSi{sub 2}O{sub 7} is reported as two polymorphs, one is a new structure type. • Crystals synthesized out of molten fluoride fluxes.« less

Ordered distribution of I and Cl in the low-temperature crystal structure of mutnovskite, Pb{sub 4}As{sub 2}S{sub 6}ICl: An X-ray single-crystal study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bindi, Luca; Garavelli, Anna; Pinto, Daniela

2008-02-15

To study the temperature-dependent structural changes and to analyze the crystal chemical behavior of the halogens as a function of temperature, a crystal of the recently discovered mineral mutnovskite, ideally Pb{sub 2}AsS{sub 3}(I,Cl,Br), has been investigated by X-ray single-crystal diffraction methods at 300 and 110 K. At room temperature (RT) mutnovskite was confirmed to possess a centrosymmetric structure-type, space group Pnma, while at low temperature (110 K) it adopts a non-centrosymmetric orthorhombic structure-type, space group Pnm2{sub 1}, with a=11.5394(9) A, b=6.6732(5) A, c=9.3454(7) A, V=719.64(9) A{sup 3} and Z=2. Mutnovskite reconverts to the centrosymmetric-type upon returning to RT thus indicatingmore » that the phase transition is completely reversible in character. The refinement of the LT-structure leads to a residual factor R=0.0336 for 1827 independent observed reflections [F{sub o}>4{sigma}(F{sub o})] and 80 variables. The crystal structure of cooled mutnovskite is topologically identical to that observed at RT and the slight structural changes occurring during the phase transition Pnma{yields}Pnm2{sub 1} are mainly restricted to the coordination polyhedra around Pb. The structure solution revealed that I and Cl are ordered into two specific sites. Indeed, the unique mixed (I,Cl) position in the RT-structure (Wyckoff position 4c) transforms into two 2a Wyckoff positions in the LT-structure hosting I and Cl, respectively. - Graphical abstract: In the crystal structure of mutnovskite at 110 K the two halogens I and Cl are ordered into two specific sites and only slight changes in the coordination environment around Pb atoms occur during the phase transition Pnma{yields}Pnm2{sub 1} from the RT-structure to the LT-structure. Two kinds of layers alternating along a are present in the LT-structure: Layer I contains Cl atoms and [001] columns of Pb1 and Pb4 prisms, layer II contains I atoms and [001] columns of Pb2 and Pb3 prisms.« less

Ferroelectric performances and crystal structures of (Pb, La)(Zr, Ti, Nb)O{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kitamura, Naoto; Division of Ecosystem Research, Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510; Mizoguchi, Takuma

2014-02-15

In this study, we focused on Nb and La substituted Pb(Zr, Ti)O{sub 3}: i.e., (Pb, La)(Zr, Ti, Nb)O{sub 3}. As for the samples, dependences of ferroelectric properties on La and Nb compositions were examined. In addition, the crystal structures were analyzed by the Rietveld method, and then a relationship between the metal compositions and the crystal structures were discussed. From P–E hysteresis loop measurements, it was found that the remanant polarization of Pb(Zr, Ti)O{sub 3} was increased by both the La and Nb substitutions although the heavy substitution of La had an undesirable effect. It was also indicated that themore » Curie temperature decreased with increasing La content. The Rietveld analysis using synchrotron X-ray diffraction patterns demonstrated that the structure distortion was relaxed by the La and Nb substitutions. Such a change in the crystals was well consistent with the harmful effects on the Curie temperature and the remanent polarization by the heavy La substitution. - Graphical abstract: Rietveld refinement pattern of 2 mol% PbSiO{sub 3}-added Pb{sub 0.95}La{sub 0.05}Zr{sub 0.50}Ti{sub 0.45}Nb{sub 0.05}O{sub 3} (synchrotron X-ray diffraction). Display Omitted - Highlights: • (Pb,La)(Zr,Ti,Nb)O{sub 3} were successfully synthesized. • Remanant polarization of Pb(Zr,Ti)O{sub 3} was improved by substitutions of La and Nb. • Crystal structures of (Pb,La)(Zr,Ti,Nb)O{sub 3} were refined and the distortions were estimated.« less

Passive Sensor Materials Based on Liquid Crystals

DTIC Science & Technology

2011-03-12

REPORT Passive Sensor Materials based on Liquid Crystals 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: Research supported by this grant entitled “Passive...Sensor Materials Based on Liquid Crystals” revolved around an investigation of liquid crystalline materials for use in passive sensors for chemical... based on Liquid Crystals Report Title ABSTRACT Research supported by this grant entitled “Passive Sensor Materials Based on Liquid Crystals” revolved

Bismuth zinc vanadate, BiZn{sub 2}VO{sub 6}: New crystal structure type and electronic structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eliziario Nunes, Sayonara; Department of Materials Engineering, Federal University of São Carlos, 13565-905 São Carlos, SP; Wang, Chun-Hai

2015-02-15

We report a combined experimental and computational study of the crystal structure and electronic properties of bismuth zinc vanadate, BiZn{sub 2}VO{sub 6}, known for its visible light photocatalytic activity. The crystal structure has been solved from laboratory powder X-ray diffraction data using the repeated minimisations from random starting values method. BiZn{sub 2}VO{sub 6} adopts a new structure type, based on the following building blocks: corner- and edge-sharing ZnO{sub 4} tetrahedra, ZnO{sub 6} octahedra and VO{sub 4} tetrahedra, and Bi{sub 2}O{sub 12} dimers. It is the only known member of the BiM{sub 2}AO{sub 6} (M=Pb, Ca, Cd, Mn, Zn, Mg, Cu;more » A=V, P, As) family which does not appear to be structurally closely related to others. The electronic structure of BiZn{sub 2}VO{sub 6}, calculated by DFT methods, shows that it is an indirect gap semiconductor with a calculated band gap of 1.6 eV, which compares favourably to the experimentally measured value of 2.4 eV. - Graphical abstract: The crystal structure of BiZn{sub 2}VO{sub 6}, a new structure type in the BiM{sub 2}AO{sub 6} (M=Mg, Ca, Cd, Cu, Pb, Mn, Zn; A=V, P, As) family. - Highlights: • Structure solution from PXRD data by repeated minimisations from random starting values. • New structure type in the BiM{sub 2}AO{sub 6} (M=Pb, Ca, Cd, Mn, Zn, Mg, Cu; A=V, P, As) family. • Electronic structure calculation.« less

Crystal growth of incommensurate members of 2H-hexagonal perovskite related oxides: Ba{sub 4}M{sub z}Pt{sub 3−z}O{sub 9} (M=Co, Ni, Cu, Zn, Mg, Pt)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferreira, Timothy; Morrison, Gregory; Yeon, Jeongho

2016-04-15

Millimeter sized crystals of six oxides of approximate composition Ba{sub 4}M{sub z}Pt{sub 3-z}O{sub 9} (M=Co, Ni, Cu, Zn, Mg, Pt) were grown from molten K{sub 2}CO{sub 3} fluxes and found to crystallize in a 2H hexagonal perovskite-related structure type. The compositions of these incommensurate structures, which belong to the A{sub 3n+3m}A′{sub n}B{sub 3m+n}O{sub 9m+6n} family of 2H hexagonal perovskite related oxides, were characterized by X-ray diffraction, energy dispersive spectroscopy, and magnetic susceptibility measurements. The specific synthetic considerations, crystal growth conditions, and magnetic susceptibility measurements are discussed. - Graphical abstract: SEM image and average commensurate unit cell of Ba{sub 4}Pt{sub 3}O{submore » 9.} - Highlights: • Single crystals of the series Ba{sub 4}A′{sub z}Pt{sub 3-z}O{sub 9} were grown via a molten carbonate flux. • Ba{sub 4}Pt{sub 3}O{sub 9} and all substitutional variants are incommensurate, composite structures. • All compounds have an approximate stoichiometry of Ba{sub 4}A′Pt{sub 2}O{sub 9.}.« less

Structural insights into simocyclinone as an antibiotic, effector ligand and substrate

PubMed Central

Buttner, Mark J; Schäfer, Martin; Lawson, David M

2017-01-01

Abstract Simocyclinones are antibiotics produced by Streptomyces and Kitasatospora species that inhibit the validated drug target DNA gyrase in a unique way, and they are thus of therapeutic interest. Structural approaches have revealed their mode of action, the inducible-efflux mechanism in the producing organism, and given insight into one step in their biosynthesis. The crystal structures of simocyclinones bound to their target (gyrase), the transcriptional repressor SimR and the biosynthetic enzyme SimC7 reveal fascinating insight into how molecular recognition is achieved with these three unrelated proteins. PMID:29126195

A general representation scheme for crystalline solids based on Voronoi-tessellation real feature values and atomic property data

PubMed Central

Jalem, Randy; Nakayama, Masanobu; Noda, Yusuke; Le, Tam; Takeuchi, Ichiro; Tateyama, Yoshitaka; Yamazaki, Hisatsugu

2018-01-01

Abstract Increasing attention has been paid to materials informatics approaches that promise efficient and fast discovery and optimization of functional inorganic materials. Technical breakthrough is urgently requested to advance this field and efforts have been made in the development of materials descriptors to encode or represent characteristics of crystalline solids, such as chemical composition, crystal structure, electronic structure, etc. We propose a general representation scheme for crystalline solids that lifts restrictions on atom ordering, cell periodicity, and system cell size based on structural descriptors of directly binned Voronoi-tessellation real feature values and atomic/chemical descriptors based on the electronegativity of elements in the crystal. Comparison was made vs. radial distribution function (RDF) feature vector, in terms of predictive accuracy on density functional theory (DFT) material properties: cohesive energy (CE), density (d), electronic band gap (BG), and decomposition energy (Ed). It was confirmed that the proposed feature vector from Voronoi real value binning generally outperforms the RDF-based one for the prediction of aforementioned properties. Together with electronegativity-based features, Voronoi-tessellation features from a given crystal structure that are derived from second-nearest neighbor information contribute significantly towards prediction. PMID:29707064

Synthesis of new structurally related cyanamide compounds LiM(CN{sub 2}){sub 2} where M is Al{sup 3+}, In{sup 3+} or Yb{sup 3+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kubus, Mariusz, E-mail: mariusz.kubus@anorg.uni-tuebingen.de; Heinicke, Robert; Ströbele, Markus

2015-02-15

Highlights: • New cyanamide compounds LiM(CN{sub 2}){sub 2} where M is Al{sup 3+}, In{sup 3+} or Yb{sup 3+}. • New luminescent material LiIn(CN{sub 2}){sub 2}:Tb{sup 3+}. • Reduction in efficiency of luminescence with temperature increase. - Abstract: New ternary cyanamide compounds isostructural to LiY(CN{sub 2}){sub 2} were obtained by solid state metathesis reaction. The crystal structure of LiAl(CN{sub 2}){sub 2} was determined by single crystal X-ray diffraction, the structures of LiIn(CN{sub 2}){sub 2} and LiYb(CN{sub 2}){sub 2} were solved from X-ray powder diffraction data. Photoluminescence properties of Tb{sup 3+}-doped LiIn(CN{sub 2}){sub 2} are reported too.

Crystal structure of NucB, a biofilm-degrading endonuclease

PubMed Central

Baslé, Arnaud; Hewitt, Lorraine; Koh, Alan; Lamb, Heather K; Thompson, Paul; Burgess, J Grant; Hall, Michael J; Hawkins, Alastair R; Murray, Heath

2018-01-01

Abstract Bacterial biofilms are a complex architecture of cells that grow on moist interfaces, and are held together by a molecular glue of extracellular proteins, sugars and nucleic acids. Biofilms are particularly problematic in human healthcare as they can coat medical implants and are thus a potential source of disease. The enzymatic dispersal of biofilms is increasingly being developed as a new strategy to treat this problem. Here, we have characterized NucB, a biofilm-dispersing nuclease from a marine strain of Bacillus licheniformis, and present its crystal structure together with the biochemistry and a mutational analysis required to confirm its active site. Taken together, these data support the categorization of NucB into a unique subfamily of the ββα metal-dependent non-specific endonucleases. Understanding the structure and function of NucB will facilitate its future development into an anti-biofilm therapeutic agent. PMID:29165717

International Congress on Glass XII (in several languages)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doremus, R H; LaCourse, W C; Mackenzie, J D

1980-01-01

A total of 158 papers are included under nine headings: structure and glass formation; optical properties; electrical and magnetic properties; mechanical properties and relaxation; mass transport; chemical durability and surfaces; nucleation; crystallization; and glass ceramics; processing; and automatic controls. Separate abstracts were prepared for eight papers; four of the remaining papers had been processed previously for the data base. (DLC)

Synthesis, crystal structure and electrical properties of the tetrahedral quaternary chalcogenides CuM{sub 2}InTe{sub 4} (M=Zn, Cd)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nolas, George S., E-mail: gnolas@usf.edu; Hassan, M. Shafiq; Dong, Yongkwan

Quaternary chalcogenides form a large class of materials that continue to be of interest for energy-related applications. Certain compositions have recently been identified as possessing good thermoelectric properties however these materials typically have the kesterite structure type with limited variation in composition. In this study we report on the structural, optical and electrical properties of the quaternary chalcogenides CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} which crystallize in the modified zinc-blende crystal structure, and compare their properties with that of CuZn{sub 2}InSe{sub 4}. These p-type semiconductors have direct band gaps of about 1 eV resulting in relatively high Seebeck coefficientmore » and resistivity values. This work expands on the research into quaternary chalcogenides with new compositions and structure types in order to further the fundamental investigation of multinary chalcogenides for potential thermoelectrics applications. - Graphical abstract: The structural, optical and electrical properties of the quaternary chalcogenides CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} are reported for the first time. The unique crystal structure allows for relatively good electrical transports and therefore potential for thermoelectric applications. - Highlights: • The physical properties of CuZn{sub 2}InTe{sub 4} and CuCd{sub 2}InTe{sub 4} are reported for the first time. • These materials have potential for thermoelectric applications. • Their direct band gaps also suggest potential for photovoltaics applications.« less

Structural, magnetic, magneto-caloric and Mössbauer spectral study of Tb{sub 2}Fe{sub 17} compound synthesized by arc melting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Charfeddine, S.; LVMU, Centre National de Recherches en Sciences des Matériaux, Technopole de Borj-Cédria, BP 73 Soliman 8027; Zehani, K.

We have synthesized the intermetallic Tb{sub 2}Fe{sub 17} compound in hexagonal crystal structure by arc-melting without annealing. X-ray diffraction pattern has been refined by Rietveld method. The crystal structure is hexagonal with P6{sub 3}/mmc space group (Th{sub 2}Ni{sub 17}-type). The Mössbauer spectrum of Tb{sub 2}Fe{sub 17} compound has been analyzed with seven magnetic sextets assigned to the inequivalent crystallographic sites. The temperature dependence of magnetization data revealed that Tb{sub 2}Fe{sub 17} exhibits a second-order ferromagnetic to paramagnetic phase transition in the vicinity of Curie temperature (T{sub C}=412 K). The relative cooling power around the magnetic transition and the Arrott plotsmore » are also reported. - Graphical abstract: A 3D surface showing the temperature and applied magnetic field dependencies of the magnetization for Tb{sub 2}Fe{sub 17} compound (left). Rietveld analysis of the XRD pattern (right). Crystal structure for the hexagonal P6{sub 3}/mmc Tb{sub 2}Fe{sub 17} (bottom). Display Omitted - Highlights: • Tb{sub 2}Fe{sub 17} single-phase synthesized by simple arc-melting without any heat treatment. • The crystal structure is hexagonal with P6{sub 3}/mmc space group. • The magnetic entropy change of the sample was determined by Maxwell relation. • Hyperfine parameters, magnetic and magnetocaloric properties were studied.« less

Structural and spectroscopic properties of pure and doped LiCe(PO{sub 3}){sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abdelhedi, M., E-mail: m_abdelhedi2002@yahoo.fr; Horchani-Naifer, K.; Dammak, M.

2015-10-15

Graphical abstract: Emission and excitation and spectra of Eu{sup 3+} doped LiCe(PO{sub 3}){sub 4} host lattice with 1, 2, 3 and 4 mol%. - Highlights: • Europium–doped LiCe(PO{sub 3}){sub 4} were prepared by flux method. • It was analyzed by infrared and Raman spectroscopy, and luminescence spectroscopy. • LiCe(PO{sub 3}){sub 4} doped with Eu{sup 3+} ions as luminophore host materials to produce an intense red. - Abstract: Single crystals of LiCe(PO{sub 3}){sub 4} polyphosphate have been synthesized by the flux method and its structural and luminescence properties have been investigated. This compound crystallizes in the space group C2/c with unitmore » cell dimensions a = 16.52(7) Å, b = 7.09(4) Å, c = 9.83 (4)Å, β = 126.29(4)°, Z = 8 and V = 927.84(3) Å{sup 3}. The obtained polytetraphosphate exhibits very small crystals and the dopant Eu{sup 3+} ions were successfully incorporated into the sites of Ce{sup 3+} ions of the host lattice. The spectroscopy properties confirm the potentiality of present LiCe(PO{sub 3}){sub 4} doped with Eu{sup 3+} ions as luminophore host materials to produce an intense red luminescence at 628 nm corresponding to {sup 5}D{sub 0} → {sup 7}F{sub 2} emission level and have significant importance in the development of emission optical systems.« less

Structure and phase formation behavior and dielectric and magnetic properties of lead iron tantalate-lead zirconate titanate multiferroic ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wongmaneerung, R., E-mail: re_nok@yahoo.com; Tipakontitikul, R.; Jantaratana, P.

2016-03-15

Highlights: • The multiferroic ceramics consisted of PFT and PZT. • Crystal structure changed from cubic to mixedcubic and tetragonal with increasing PZT content. • Dielectric showed the samples underwent a typical relaxor ferroelectric behavior. • Magnetic properties showed very interesting behavior with square saturated magnetic hysteresis loops. - Abstract: Multiferroic (1 − x)Pb(Fe{sub 0.5}Ta{sub 0.5})O{sub 3}–xPb(Zr{sub 0.53}Ti{sub 0.47})O{sub 3} (or PFT–PZT) ceramics were synthesized by solid-state reaction method. The crystal structure and phase formation of the ceramics were examined by X-ray diffraction (XRD). The local structure surrounding Fe and Ti absorbing atoms was investigated by synchrotron X-ray Absorption Near-Edgemore » Structure (XANES) measurement. Dielectric properties were studied as a function of frequency and temperature using a LCR meter. A vibrating sample magnetometer (VSM) was used to determine the magnetic hysteresis loops. XRD study indicated that the crystal structure of the sample changed from pure cubic to mixed cubic and tetragonal with increasing PZT content. XANES measurements showed that the local structure surrounding Fe and Ti ions was similar. Dielectric study showed that the samples underwent a typical relaxor ferroelectric behavior while the magnetic properties showed very interesting behavior with square saturated magnetic hysteresis loops.« less

Crystallization processes in Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Svoboda, Roman, E-mail: roman.svoboda@upce.cz; Bezdička, Petr; Gutwirth, Jan

2015-01-15

Highlights: • Crystallization kinetics of Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass was studied in dependence on particle size by DSC. • All studied fractions were described in terms of the SB autocatalytic model. • Relatively high amount of Te enhances manifestation of bulk crystallization mechanisms. • XRD analysis of samples crystallized under different conditions showed correlation with DSC data. • XRD analysis revealed a new crystallization mechanism indistinguishable by DSC. - Abstract: Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis were used to study crystallization in Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass under non-isothermal conditions as a function of the particlemore » size. The crystallization kinetics was described in terms of the autocatalytic Šesták–Berggren model. An extensive discussion of all aspects of a full-scale kinetic study of a crystallization process was undertaken. Dominance of the crystallization process originating from mechanically induced strains and heterogeneities was confirmed. Substitution of Se by Te was found to enhance the manifestation of the bulk crystallization mechanisms (at the expense of surface crystallization). The XRD analysis showed significant dependence of the crystalline structural parameters on the crystallization conditions (initial particle size of the glassy grains and applied heating rate). Based on this information, a new microstructural crystallization mechanism, indistinguishable by DSC, was proposed.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chuvashova, Irina, E-mail: irina.chuvashova@gmail.com; Bayerisches Geoinstitut, University of Bayreuth, D-95440 Bayreuth; Bykova, Elena

In the present study single crystals of rhombohedral α-B were investigated under pressure to 60 GPa by means of single-crystal X-ray diffraction. The bulk modulus of α-B was found to be K=224(7) GPa (K′=3.0(3)). Measurements of interatomic distances as a function of pressure revealed that the intericosahedral two-center two-electron (2c–2e) bonds are almost as stiff as some of intraicosahedral ones. The three-center two-electron (3c–2e) intericosahedral bonds show much higher compliance compared to other bonds in α-B. The vibrational properties of α-B under pressure were investigated by Raman spectroscopy at pressures up to 160 GPa and IR spectroscopy at pressures upmore » to 53 GPa. - Graphical abstract: The rhombohedral α-B is highly incompressible and extremely stable: it maintains its crystal structure up to 160 GPa and its intericosahedral 2e2c bonds are almost as stiff as some of intraicosahedral ones. - Highlights: • Structural stability of α-B has been investigated up to 160 GPa on single crystals. • Single-crystal x-ray diffraction reveals that α-B is highly incompressible. • Compressibility of B{sub 12} icosahedra is considerably lower than that of the bulk material. • Intericosahedral 2e2c bonds are almost as stiff as some of intraicosahedral ones.« less

Solution‐crystallization and related phenomena in 9,9‐dialkyl‐fluorene polymers. II. Influence of side‐chain structure

PubMed Central

Perevedentsev, Aleksandr; Stavrinou, Paul N.; Smith, Paul

2015-01-01

ABSTRACT Solution‐crystallization is studied for two polyfluorene polymers possessing different side‐chain structures. Thermal analysis and temperature‐dependent optical spectroscopy are used to clarify the nature of the crystallization process, while X‐ray diffraction and scanning electron microscopy reveal important differences in the resulting microstructures. It is shown that the planar‐zigzag chain conformation termed the β‐phase, which is observed for certain linear‐side‐chain polyfluorenes, is necessary for the formation of so‐called polymer‐solvent compounds for these polymers. Introduction of alternating fluorene repeat units with branched side‐chains prevents formation of the β‐phase conformation and results in non‐solvated, i.e. melt‐crystallization‐type, polymer crystals. Unlike non‐solvated polymer crystals, for which the chain conformation is stabilized by its incorporation into a crystalline lattice, the β‐phase conformation is stabilized by complexation with solvent molecules and, therefore, its formation does not require specific inter‐chain interactions. The presented results clarify the fundamental differences between the β‐phase and other conformational/crystalline forms of polyfluorenes. © 2015 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 1492–1506 PMID:27546983

The synthesis, single-crystal structure, optical absorption, and resistivity of Th{sub 2}GeSe{sub 5}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koscielski, Lukasz A.; Malliakas, Christos D.; Sarjeant, Amy A.

2013-09-15

The compound Th{sub 2}GeSe{sub 5} has been synthesized by the reaction of the elements at 1273 K. From a single-crystal study Th{sub 2}GeSe{sub 5} crystallizes in the Ba{sub 5}Si{sub 3} structure type with four formula units in the space group D{sup 8}{sub 4h}−P4/ncc of the tetragonal system in a cell with dimensions a=7.4968(4) Å and c=13.6302(9) Å at 100(2) K. From optical absorption measurements Th{sub 2}GeSe{sub 5} is found to have an optical band gap of 1.92 eV (indirect) or 1.98 eV (direct), consistent with its red color. Th{sub 2}GeSe{sub 5} is a wide gap semiconductor, as indicated by itsmore » electrical resistivity at 298 K of 4.37(2)×10{sup 9} Ω cm measured on a single crystal. - Graphical abstract: The structure of Th{sub 2}GeSe{sub 5}. Display Omitted - Highlights: • The new compound Th{sub 2}GeSe{sub 5} was synthesized from the elements and recrystallized from Sb{sub 2}Se{sub 3}. • Th{sub 2}GeSe{sub 5} crystallizes in the Ba{sub 5}Si{sub 3} structure type. • The band gap of Th{sub 2}GeSe{sub 5} is1.92 eV and its resistivity shows it to be a wide gap semiconductor.« less

Studies on the growth, structural, optical, mechanical properties of 8-hydroxyquinoline single crystal by vertical Bridgman technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhakaran, SP.; Babu, R. Ramesh, E-mail: rampap2k@yahoo.co.in; Velusamy, P.

2011-11-15

Highlights: {yields} Growth of bulk single crystal of 8-hydroxyquinoline (8-HQ) by vertical Bridgman technique for the first time. {yields} The crystalline perfection is reasonably good. {yields} The photoluminescence spectrum shows that the material is suitable for blue light emission. -- Abstract: Single crystal of organic nonlinear optical material, 8-hydroxyquinoline (8-HQ) of dimension 52 mm (length) x 12 mm (dia.) was grown from melt using vertical Bridgman technique. The crystal system of the material was confirmed by powder X-ray diffraction analysis. The crystalline perfection of the grown crystal was examined by high-resolution X-ray diffraction study. Low angular spread around 400'' ofmore » the diffraction curve and the low full width half maximum values show that the crystalline perfection is reasonably good. The recorded photoluminescence spectrum shows that the material is suitable for blue light emission. Optical transmittance for the UV and visible region was measured and mechanical strength was estimated from Vicker's microhardness test along the growth face of the grown crystal.« less

CRYSTAL POLYMORPHISM IN 1-BUTYL-3-METHYLIMIDAZOLIUM HALIDES: SUPPORTING IONIC LIQUID FORMATION THROUGH INHIBITION OF CRYSTALLIZATION. (R828257)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Hydrothermal synthesis, crystal structure and properties of 2-D and 3-D lanthanide sulfates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu Yan; Ding Shaohua; Zheng Xuefang

2007-07-15

Two new lanthanum sulfates DySO{sub 4}(OH) 1 and Eu{sub 2}(SO{sub 4}){sub 3}(H{sub 2}O){sub 8} 2 have been hydrothermally synthesized. The colorless crystals were characterized by IR, TGA, ICP and XRD. The structure was determined by single-crystal X-ray diffraction. 1 crystallizes with monoclinic symmetry, space group P2(1)/n [a=7.995(4) A, b=10.945(5) A, c=8.164(4) A, {alpha}=90{sup o}, {beta}=93.619(6){sup o}, {gamma}=90{sup o}, V=713.0(5) A{sup 3}, Z=8]. It displays a three-dimensional framework, based on the novel Dy-O chains connected by the sulfate groups through helical chains. 2 crystallizes with monoclinic symmetry, space group C2/c, [a=13.5605(17) A, b=6.7676(8) A, c=18.318(2) A, {alpha}=90{sup o}, {beta}=102.265(2){sup o}, {gamma}=90{supmore » o}, V=1642.7 (4) A{sup 3}, Z=4]. Its layered framework is attained by the europium atoms connected by the sulfate groups arranged in a helical manner. - Graphical abstract: Two new lanthanum sulfates DySO{sub 4}(OH) 1 and Eu{sub 2} (SO{sub 4}){sub 3} (H{sub 2}O){sub 8} 2 have been hydrothermally synthesized. The colorless crystals were characterized by IR, TGA, ICP and XRD. The structure was determined by single-crystal X-ray diffraction. It displays a three dimensional framework, based on the novel Dy-O chains connected by the sulfate groups through helical chains.« less

Solvothermal indium fluoride chemistry: Syntheses and crystal structures of K{sub 5}In{sub 3}F{sub 14}, beta-(NH{sub 4}){sub 3}InF{sub 6} and [NH{sub 4}]{sub 3}[C{sub 6}H{sub 21}N{sub 4}]{sub 2}[In{sub 4}F{sub 21}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jayasundera, Anil C.A.; Goff, Richard J.; Li Yang

2010-02-15

The solvothermal syntheses and crystal structures of three indium fluorides are presented. K{sub 5}In{sub 3}F{sub 14} (1) and beta-(NH{sub 4}){sub 3}InF{sub 6} (2) are variants on known inorganic structure types chiolite and cryolite, respectively, with the latter exhibiting a complex and apparently novel structural distortion. [NH{sub 4}]{sub 3}[C{sub 6}H{sub 21}N{sub 4}]{sub 2}[In{sub 4}F{sub 21}] (3) represents a new hybrid composition displaying a unique trimeric metal fluoride building unit. - Graphical abstract: Solvothermal synthesis has been used to prepare three indium fluorides, including a novel hybrid material containing a unique [In{sub 3}F{sub 15}] trimer templated by tren.

Crystal structure and low-energy Einstein mode in ErV{sub 2}Al{sub 20} intermetallic cage compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winiarski, Michał J., E-mail: mwiniarski@mif.pg.gda.pl; Klimczuk, Tomasz

Single crystals of a new ternary aluminide ErV{sub 2}Al{sub 20} were grown using a self-flux method. The crystal structure was determined by powder X-ray diffraction measurements and Rietveld refinement, and physical properties were studied by means of electrical resistivity, magnetic susceptibility and specific heat measurements. These measurements reveal that ErV{sub 2}Al{sub 20} is a Curie-Weiss paramagnet down to 1.95 K with an effective magnetic moment μ{sub eff} =9.27(1) μ{sub B} and Curie-Weiss temperature Θ{sub CW} =−0.55(4) K. The heat capacity measurements show a broad anomaly at low temperatures that is attributed to the presence of a low-energy Einstein mode withmore » characteristic temperature Θ{sub E} =44 K, approximately twice as high as in the isostructural ‘Einstein solid’ VAl{sub 10.1}. - Graphical abstract: A low-energy Einstein mode is observed in a novel intermetallic cage compound ErV{sub 2}Al{sub 20} by specific heat and resistivity measurements. - Highlights: • Single crystals of a new compound ErV{sub 2}Al{sub 20} were grown by self-flux method. • Crystal structure is reported, based on powder x-ray diffraction. • ErV{sub 2}Al{sub 20} is a Curie-Weiss paramagnet. • Low-energy ‘rattling’ phonon mode (Θ{sub E}=44 K) is found in specific heat measurements.« less

Lattice thermal expansion and solubility limits of neodymium-doped ceria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jinhua, E-mail: jhzhang1212@126.com; State Key laboratory of Geological Process and Mineral Resources, China University of Geosciences, Wuhan 430074; Ke, Changming

2016-11-15

Nd{sub x}Ce{sub 1−x}O{sub 2−0.5x} (x=0–1.0) powders were prepared by reverse coprecipitation-calcination method and characterized by XRD. The crystal structure of product powders transformed from single fluorite structure to the complex of fluorite and C-type cubic structure, and finally to trigonal structure with the increase of x-value. An empirical equation simulating the lattice parameter of neodymium doped ceria was established based on the experimental data. The lattice parameters of the fluorite structure solid solutions increased with extensive adoption of Nd{sup 3+}, and the heating temperature going up. The average thermal expansion coefficients of neodymium doped ceria with fluorite structure are highermore » than 13.5×10{sup −6} °C{sup −1} from room temperature to 1200 °C. - Graphical abstract: The crystal structure of Nd{sub x}Ce{sub 1−x}O{sub 2−0.5x} (x=0–1.0) powders transformed from single fluorite structure to the complex of fluorite and C-type cubic structure, and finally to trigonal structure with the increase of x-value.« less

Synthesis and Structural Features of [4,4'-Diisopropoxyester-2,2'-bipyridine], [Dichloro(4,4'-diisopropoxyester-2,2'-bi-pyridine)-platinum(ii)] and Its Dichloromethane Solvated Pseudo-Polymorph: Versatile Supramolecular Interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Browning, Charles; Nesterov, Vladimir N.; Wang, Xiaoping

We report that the organic ligand 4,4'-diisopropoxyester-2,2'-bipyridine, C 18H 20N 2O 4 (1), crystallizes in the triclinic crystal system P-1 and the molecule occupies a special position in the unit cell. In the crystal, molecules form stacks with partial overlapping of the pyridine rings. The Pt(II) dichloro complex of 1 crystallizes from a mixture of ethanol/hexane and from dichloromethane to form orange and yellow crystals, respectively. The orange non-solvated crystals of the (bipyridine)(dichloro)platinum(II) complex C 18H 20N 2O 4PtCl 2 (2) crystallize in the triclinic crystal system P-1 as well with two independent molecules in the unit cell. In themore » crystal packing, molecules form two types of dimers with Pt1 ··· Pt1A and Pt2···Pt2A distances of 3.478 and 5.186 angstrom respectively. The yellow crystals, as a solvated pseudo-polymorph C 18H 20N 2O 4PtCl 2·1.5 CH 2Cl 2 (3) also crystallize in the triclinic crystal system P-1 with two independent molecules in the unit cell. In the crystal packing, molecules form Pt2 ···Pt1 ···Pt1A ···Pt2A intermolecular contacts with alternating distances 3.501 and 3.431 angstrom, respectively, forming infinite chains. Graphical Abstract The dichloro(bipyridine)platinum complex, dichloro(4,4'-diisopropoxyester-2,2'-bipyridine)platinum(II), forms single crystals as a stable non-solvated form and a solvated polymorph with dramatically different supramolecular structure and short contacts.« less

Synthesis and Structural Features of [4,4'-Diisopropoxyester-2,2'-bipyridine], [Dichloro(4,4'-diisopropoxyester-2,2'-bi-pyridine)-platinum(ii)] and Its Dichloromethane Solvated Pseudo-Polymorph: Versatile Supramolecular Interactions

DOE PAGES

Browning, Charles; Nesterov, Vladimir N.; Wang, Xiaoping; ...

2015-06-03

We report that the organic ligand 4,4'-diisopropoxyester-2,2'-bipyridine, C 18H 20N 2O 4 (1), crystallizes in the triclinic crystal system P-1 and the molecule occupies a special position in the unit cell. In the crystal, molecules form stacks with partial overlapping of the pyridine rings. The Pt(II) dichloro complex of 1 crystallizes from a mixture of ethanol/hexane and from dichloromethane to form orange and yellow crystals, respectively. The orange non-solvated crystals of the (bipyridine)(dichloro)platinum(II) complex C 18H 20N 2O 4PtCl 2 (2) crystallize in the triclinic crystal system P-1 as well with two independent molecules in the unit cell. In themore » crystal packing, molecules form two types of dimers with Pt1 ··· Pt1A and Pt2···Pt2A distances of 3.478 and 5.186 angstrom respectively. The yellow crystals, as a solvated pseudo-polymorph C 18H 20N 2O 4PtCl 2·1.5 CH 2Cl 2 (3) also crystallize in the triclinic crystal system P-1 with two independent molecules in the unit cell. In the crystal packing, molecules form Pt2 ···Pt1 ···Pt1A ···Pt2A intermolecular contacts with alternating distances 3.501 and 3.431 angstrom, respectively, forming infinite chains. Graphical Abstract The dichloro(bipyridine)platinum complex, dichloro(4,4'-diisopropoxyester-2,2'-bipyridine)platinum(II), forms single crystals as a stable non-solvated form and a solvated polymorph with dramatically different supramolecular structure and short contacts.« less

Crystal structure of TBC1D15 GTPase‐activating protein (GAP) domain and its activity on Rab GTPases

PubMed Central

Chen, Yan‐Na; Gu, Xin; Zhou, X. Edward; Wang, Weidong; Cheng, Dandan; Ge, Yinghua; Ye, Fei

2017-01-01

Abstract TBC1D15 belongs to the TBC (Tre‐2/Bub2/Cdc16) domain family and functions as a GTPase‐activating protein (GAP) for Rab GTPases. So far, the structure of TBC1D15 or the TBC1D15·Rab complex has not been determined, thus, its catalytic mechanism on Rab GTPases is still unclear. In this study, we solved the crystal structures of the Shark and Sus TBC1D15 GAP domains, to 2.8 Å and 2.5 Å resolution, respectively. Shark‐TBC1D15 and Sus‐TBC1D15 belong to the same subfamily of TBC domain‐containing proteins, and their GAP‐domain structures are highly similar. This demonstrates the evolutionary conservation of the TBC1D15 protein family. Meanwhile, the newly determined crystal structures display new variations compared to the structures of yeast Gyp1p Rab GAP domain and TBC1D1. GAP assays show that Shark and Sus GAPs both have higher catalytic activity on Rab11a·GTP than Rab7a·GTP, which differs from the previous study. We also demonstrated the importance of arginine and glutamine on the catalytic sites of Shark GAP and Sus GAP. When arginine and glutamine are changed to alanine or lysine, the activities of Shark GAP and Sus GAP are lost. PMID:28168758

Sulfur hexafluoride plasma surface modification of Gly-Ala and Ala-Gly as Bombyx mori silk model compounds: Mechanism investigations

NASA Astrophysics Data System (ADS)

Sangprasert, W.; Lee, V. S.; Boonyawan, D.; Tashiro, K.; Nimmanpipug, P.

2010-01-01

Low-pressure plasma has been used to improve the hydrophobicity of Thai silk. In this study, Glycine-Alanine (GA) and Alanine-Glycine (AG) were chosen to represent model compounds of Bombyx mori silk. Single crystals of the simplified model compounds were characterized by polarizing microscopy and X-ray diffraction. The space groups of P2 12 12 1 and P2 1 were found for AG and GA, respectively. The initial structures for calculation were obtained from the experimental crystal structures. Density functional theory at the BHandHLYP levels was used to investigate possible mechanisms of fluorine radicals reacting with AG and GA in the SF 6 plasma treatment. The results indicate that hydrogen atoms of silk model compounds were most likely to be abstracted from the alanine residue.

Reply to “Structural and magnetic behavior of the cubic oxyfluoride SrFeO{sub 2}F studied by neutron diffraction”

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clemens, Oliver, E-mail: oliver.clemens@kit.edu; Karlsruher Institut für Technologie, Institut für Nanotechnologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen; Berry, Frank J.

2015-03-15

In this article we comment on the results published by Thompson et al. (, J. Solid State Chem. 219 (2014) 173–178) on the crystal structure of SrFeO{sub 2}F, who claim the compound to crystallize in the cubic space group Pm-3m. We give a more detailed explanation of the determination of our previously reported structural model with Imma symmetry (Clemens et al., J. Solid State Chem. 206 (2013) 158–169), with addition of variable temperature XRD measurements with high counting time to provide unambiguous evidence for the Imma model being correct for our sample. - Graphical abstract: The crystal structure of SrFeO{submore » 2}F is discussed with regards to previous reports. - Highlights: • SrFeO{sub 2}F was synthesized by polymer based fluorination of SrFeO{sub 3}. • Evaluation of the diffraction data shows a pseudocubic cell metric. • Superstructure reflections at low d-spacings indicate deviation from cubic symmetry. • The phase transition temperature from orthorhombic to cubic was determined using variable temperature X-ray diffraction. • Results published by Thompson et al. are critically discussed with respect to those observations.« less

Crystal chemistry of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} double monophosphates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bregiroux, Damien, E-mail: damien.bregiroux@upmc.fr; Popa, Karin; Wallez, Gilles

2015-10-15

M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds have been extensively studied for several decades for their potential applications in the field of several domains such as matrices for actinides conditioning, phosphors etc. In this paper, the relationships between composition and crystal structure of these compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. M{sup II}M′{sup IV}(PO{sub 4}){sub 2} structures stem from two different archetypes: the cheralite and the yavapaiite structures, with some exceptions that are also described in this article. The ratio of themore » cations radii appears to be the most relevant parameter. The high ratio between the ionic radii of the divalent and tetravalent cations in yavapaiite derivates results in the ordering of these cations into well-differentiated polyhedra whereas cheralite is the only non-ordered structure encountered for M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds. - Graphical abstract: In this paper, the relationships between composition and crystal structure of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. - Highlights: • Crystal structure–composition relationships of MIIM′IV(PO4)2 compounds. • Review of the various processes used for the synthesis of these compounds. • Their most reported properties are described and discussed.« less

Coding Without Your Crystal Ball: Unanticipated Object-Oriented Reuse

DTIC Science & Technology

2009-12-01

Abstract In many ways, existing languages place unrealistic expectations on library and framework designers, allowing some varieties of client reuse only...if it is explicitly— sometimes manually—supported. Instead, we should aim for the ideal: a language design that reduces the amount of prognostication...that is required on the part of the original designers. In particular, I show that languages can and should support a combination of structural and

On Predicting the Crystal Structure of Energetic Materials From Quantum Mechanics

DTIC Science & Technology

2008-12-01

DE ABSTRACT A quantum-mechanically-based potential energy function that describes interactions of dimers of the explosive ...method is capable of producing force fields for interactions of the molecular crystalline explosive RDX, and appears to be suitable to enable reliable...Ridge, TN. Byrd, E.F.C., Scuseria, G.E., Chabalowski, C.F., 2004: “An ab initio study of solid nitromethane , HMX, RDX and CL20: Successes and

Photonic Crystal/Nano-Electronic Device Structures for Large Array Thermal Imaging

DTIC Science & Technology

2007-11-19

order to improve the signal to noise ratio of the detection, a larger photocurrent is desirable. To increase the photocurrent of QWIPs , one needs to...CLASSIFICATION OF: Lattice-matched InGaAs/Inp quantum well infrared detector ( QWIP ) exhibits high photoconductive gain but un-adjustable detection wavelength...Title ABSTRACT Lattice-matched InGaAs/Inp quantum well infrared detector ( QWIP ) exhibits high photoconductive gain but un-adjustable detection

Ru(II) complexes containing chelating phosphine ligands. Synthesis, characterizatin, and x-ray crystal structures of dichlorobis (1,2-bis(diphenylphosphino)ethane)Ru(II) and the coordinatetively unsaturated trigonal-bipyramidal cation, chlorobis(1,2-bis(diphenylphosphino)ethane)Ru(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polam, J.R.; Porter, L.C.

1993-01-01

The reaction of trans-RuCl[sub 2](dppe)[sub 2] (1), with AgBF[sub 4] in tetrahydrofuran leads to abstraction of one of the halide ligands to produce the trigonal-bipyrimidal complex. [RuCl(dppe)[sub 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hou, Kun; Gao, Ziwei, E-mail: zwgao@snnu.edu.cn; Da, Min

Highlights: Black-Right-Pointing-Pointer Highly oriented and well-defined ZnO urchin-like crystals were successfully fabricated by a facile and effective hydrotherm method. Black-Right-Pointing-Pointer Polyvinylpyrrolidone- and hydrogen peroxide-assisted synthesis of ZnO could optimize its crystalline quality and the obtained ZnO have smooth surface, radial growth of morphology, obvious crystal edges and decreased defects. Black-Right-Pointing-Pointer The physicochemical properties of samples were studied by analysis of its structure, morphology, surface and optical properties. Black-Right-Pointing-Pointer This study represented a multistep mechanism based on [Zn(OH){sub 4}]{sup 2-} growth units about formation such urchin-like structure. -- Abstract: The urchin-like ZnO microcrystals with high crystallinity decomposed from [Zn(OH){sub 4}]{sup 2-}more » directly were obtained via a hydrothermal method. The morphology, particle size, crystalline structure and fluorescence of the as-prepared ZnO were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and photoluminescence (PL) analyses. The results demonstrated that the urchin-like ZnO crystals with wurtzite structure had a narrow distribution in size, which could be adjusted in the range of 30-80 {mu}m by varying reaction time. Broad visible light emission peak was also observed in the PL spectra of the synthesized ZnO products. A multistep growth process about how to form such a structure was proposed.« less

Synthesis, growth, structural and optical studies of a new organic three dimensional framework: 4-(aminocarbonyl)pyridine 4-(aminocarbonyl)pyridinium hydrogen L-malate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vijayalakshmi, A.; Vidyavathy, B., E-mail: vidyavathybalraj@gmail.com; Peramaiyan, G.

2017-02-15

4-(aminocarbonyl)pyridine 4-(aminocarbonyl)pyridinium hydrogen L-malate [(4ACP)(4ACP).(LM)] a new organic nonlinear optical (NLO) crystal was grown by the slow evaporation method. Single crystal X-ray diffraction analysis revealed that the [(4ACP)(4ACP).(LM)] crystal belongs to monoclinic crystal system, space group P2{sub 1}/n, with a three dimensional network. Thermogravimetry (TG) and differential thermal (DT) analyses showed that [(4ACP)(4ACP).(LM)] is thermally stable up to 165 °C. The optical transmittance window and the lower cut-off wavelength of [(4ACP)(4ACP).(LM)] were found out by UV–vis–NIR spectral study. The molecular structure of [(4ACP)(4ACP).(LM)] was further confirmed by FTIR spectral studies. The relative dielectric permittivity and dielectric loss were determined asmore » function of frequency and temperature. The third order nonlinear optical property of [(4ACP)(4ACP).(LM)] was studied by the Z-scan technique using a 532 nm diode pumped CW Nd:YAG laser. Nonlinear refractive index, nonlinear absorption coefficient and third order nonlinear susceptibility of the grown crystal were found to be 7.38×10{sup −8} cm{sup 2}/W, 0.08×10{sup −4} cm/W and 5.36×10{sup −6} esu, respectively. The laser damage threshold value is found to be 1.75 GW/cm{sup 2} - Graphical abstract: In the crystal structure of the title complex, the asymmetric unit contains one hydrogen L-malate anion, 4-(aminocarbonyl)pyridinium cation and a neutral isonicotinamide molecule. It is stabilized by intermolecular N-H…O, C-H…O and O-H…O hydrogen bonds which generate a three dimensional network.« less

Crystal structure and properties of tetragonal EuAg{sub 4}In{sub 8} grown by metal flux technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Subbarao, Udumula; Sarkar, Sumanta; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

The compound EuAg{sub 4}In{sub 8} has been obtained as single crystals in high yield from reactions run in liquid indium. X-ray diffraction on single crystals suggests that EuAg{sub 4}In{sub 8} crystallizes in the CeMn{sub 4}Al{sub 8} structure type, tetragonal space group I4/mmm with lattice constants a=b=9.7937(2) Å and c=5.7492(2) Å. Crystal structure of EuAg{sub 4}In{sub 8} is composed of pseudo Frank–Kasper cages occupied by one europium atom in each ring, which are shared through the corner along the ab plane resulting in a three dimensional network. The magnetic susceptibility of EuAg{sub 4}In{sub 8} was measured in the temperature range 2–300more » K, which obeyed Curie–Weiss law above 50 K. Magnetic moment value calculated from the fitting indicates the presence of divalent europium, which was confirmed by X-ray absorption near edge spectroscopy. Electrical resistivity measurements suggest that EuAg{sub 4}In{sub 8} is metallic in nature with a probable Fermi liquid behavior at low temperature. - Graphical abstract: The tetragonal EuAg{sub 4}In{sub 8} has been grown as single crystals from reactions run in liquid indium. Magnetic and XANES measurements suggest divalent nature of Eu and resistivity measurements suggest metallic nature. - Highlights: • EuAg{sub 4}In{sub 8} phase having tetragonal phase is grown by metal flux technique. • Magnetic and XANES measurements exhibit divalent nature of Eu in EuAg{sub 4}In{sub 8}. • Resistivity measurement suggests metallic nature and probable Fermi liquid behavior.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ranieri, M.G.A., E-mail: gabi.ranieri@ig.com.br; Aguiar, E.C.; Cilense, M.

Highlights: • Bi{sub 4}Ti{sub 3}O{sub 12} thick films were obtained by SSR and PPM methods. • Both systems crystallize in an orthorhombic structure. • Textured characteristics were evidenced. • Grain morphology affects the P–E loops. - Abstract: Bismuth titanate powders (Bi{sub 4}Ti{sub 3}O{sub 12}-BIT) were fabricated by solid state reaction (SSR) and polymeric precursor method (PPM). From these powders, Bi{sub 4}Ti{sub 3}O{sub 12} pellets were obtained by tape-casting using plate-like templates particles prepared by a molten salt method. The BIT phase crystallizes in an orthorhombic structure type with space group Fmmm. Agglomeration of the particles, which affects the densification ofmore » the ceramic, electrical conduction and leakage current at high electric fields, was monitored by transmission electronic microscopy (TEM) analyses. FEG-SEM indicated that different shape of grains of BIT ceramics was influenced by the processing route. Both SSR and PPM methods lead to unsaturated P–E loops of BIT ceramics originating from the highly c-axis orientation and high conductivity which was affected by charge carriers flowing normally to the grain boundary of the crystal lattice.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corbey, Jordan F.; Rapko, Brian M.; Wang, Zheming

Abstract The crystal structures of americium species containing a common multi-functional phosphine oxide ligand, reported for its ability to extract f elements from acidic solutions, namely 2,6-[Ph2P(O)CH2]2C5H3-NO, L, have finally been determined after over three decades of separations studies involving these species and their surrogates. The molecular compounds Am(L)(NO3)3, Am 1:1, and [Am(L)2(NO3)][NO3]2, Am 2:1, along with their neodymium and europium analogs were synthesized and characterized using single-crystal X-ray crystallography, attenuated total reflectance Fourier transform infrared (ATR) spectroscopy and luminescence spectroscopy to provide a comprehensive comparison with new and known analogous complexes.

Peculiarities of thermoelectric half-Heusler phase formation in Gd-Ni-Sb and Lu-Ni-Sb ternary systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romaka, V.V., E-mail: romakav@lp.edu.ua; Romaka, L.; Horyn, A.

The phase equilibria in the Gd–Ni–Sb and Lu-Ni-Sb ternary systems were studied at 873 K by X-ray and metallographic analyses in the whole concentration range. The interaction of the elements in the Gd–Ni–Sb system results the formation of five ternary compounds at investigated temperature: Gd{sub 5}Ni{sub 2}Sb (Mo{sub 5}SiB{sub 2}-type), Gd{sub 5}NiSb{sub 2} (Yb{sub 5}Sb{sub 3}-type), GdNiSb (MgAgAs-type), Gd{sub 3}Ni{sub 6}Sb{sub 5} (Y{sub 3}Ni{sub 6}Sb{sub 5}-type), and GdNi{sub 0.72}Sb{sub 2} (HfCuSi{sub 2}-type). At investigated temperature the Lu-Ni-Sb system is characterized by formation of the LuNiSb (MgAgAs-type), Lu{sub 5}Ni{sub 2}Sb (Mo{sub 5}SiB{sub 2}-type), and Lu{sub 5}Ni{sub 0.56}Sb{sub 2.44} (Yb{sub 5}Sb{sub 3}-type)more » compounds. The disordering in the crystal structure of half-Heusler GdNiSb and LuNiSb was revealed by EPMA and studied by means of Rietveld refinement and DFT modeling. The performed electronic structure calculations are in good agreement with electrical transport property studies. - Graphical abstract: Crystal structure model and electron localization function of Lu{sub 5}Ni{sub 2}Sb. Display Omitted - Highlights: • Gd-Ni-Sb and Lu-Ni-Sb phase diagrams were constructed at 873 K. • GdNiSb and LuNiSb are characterized by disordered crystal structure. • Crystal structure optimization with DFT calculations confirmed crystal structure disorder in GdNiSb and LuNiSb.« less

Crystal structure and magnetic properties of '{alpha} Prime Prime -Fe{sub 16}N{sub 2}' containing residual {alpha}-Fe prepared by low-temperature ammonia nitridation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamashita, S.; Masubuchi, Y.; Nakazawa, Y.

2012-10-15

Slight enhancement of saturation magnetization to 219 A m{sup 2} kg{sup -1} was observed from 199 A m{sup 2} kg{sup -1} for the original {alpha}-Fe on the intermediate nitrided mixture of '{alpha} Prime Prime -Fe{sub 16}N{sub 2}' with residual {alpha}-Fe among the low temperature ammonia nitridation products under 5 T magnetic field at room temperature. The value changed not linearly against the yield as had been expected. Crystal structure refinement indicated that the phase similar to {alpha} Prime Prime -Fe{sub 16}N{sub 2} had deviations on its lattice constants and positional parameters, compared to previously reported values for {alpha} Prime Primemore » -Fe{sub 16}N{sub 2}. Spin-polarized total energy calculations were performed using the projector-augmented wave method as implemented in the Vienna ab-initio simulation package (VASP) to calculate magnetic moment on the refined crystal structure of the intermediate '{alpha} Prime Prime -Fe{sub 16}N{sub 2}'. The calculations supported the observed magnetization enhancement in the intermediate nitridation product. - Graphical abstract: Crystal structural parameters slightly change in the intermediate nitrided '{alpha} Prime Prime -Fe{sub 16}N{sub 2}' from those in {alpha} Prime Prime -Fe{sub 16}N{sub 2} to show the magnetization maxima in the mixture of '{alpha} Prime Prime -Fe{sub 16}N{sub 2}' and the residual {alpha}-F. Highlights: Black-Right-Pointing-Pointer Larger magnetization was observed than the value of Fe{sub 16}N{sub 2} on its intermediate nitrided mixture with residual {alpha}-Fe. Black-Right-Pointing-Pointer The enhancement was related to the crystal structural deviation from Fe{sub 16}N{sub 2} on the intermediate nitride. Black-Right-Pointing-Pointer It was supported by spin-polarized total energy calculation using the deviated structure.« less

Rietveld refinement, electronic structure and ionic conductivity of Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}F{sub 2} and Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}O ceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boughzala, Khaled, E-mail: khaledboughzala@gmail.com; Preparatory Institute for Engineering Studies, 5000 Monastir; Debbichi, Mourad

In this paper, we report the effect of the tunnel anions on the ionic conductivity of Strontium-Lanthanum silicate apatites. The Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}F{sub 2} and Sr{sub 4}La{sub 6}(SiO{sub 4}){sub 6}O ceramics were prepared by the solid state reaction method. X-ray diffraction, NMR spectroscopy and Raman measurements were performed to investigate the crystal structure and vibrational active modes. Moreover, the electronic structures of the crystals were evaluated by the first-principles quantum mechanical calculation based on the density functional theory. Finally, the ionic conductivity was studied according to the complex impedance method. - Graphical abstract: The relaxed primitive unit cellmore » for Sr{sub 4}La{sub 6}Fap. Display Omitted.« less

The uncoupling of catalysis and translocation in the viral RNA-dependent RNA polymerase

PubMed Central

Shu, Bo; Gong, Peng

2017-01-01

ABSTRACT The nucleotide addition cycle of nucleic acid polymerases includes 2 major events: the pre-chemistry active site closure leading to the addition of one nucleotide to the product chain; the post-chemistry translocation step moving the polymerase active site one position downstream on its template. In viral RNA-dependent RNA polymerases (RdRPs), structural and biochemical evidences suggest that these 2 events are not tightly coupled, unlike the situation observed in A-family polymerases such as the bacteriophage T7 RNA polymerase. Recently, an RdRP translocation intermediate crystal structure of enterovirus 71 shed light on how translocation may be controlled by elements within RdRP catalytic motifs, and a series of poliovirus apo RdRP crystal structures explicitly suggest that a motif B loop may assist the movement of the template strand in late stages of transcription. Implications of RdRP catalysis-translocation uncoupling and the remaining challenges to further elucidate RdRP translocation mechanism are also discussed. PMID:28277928

Typical intellectual engagement and cognition in old age.

PubMed

Dellenbach, Myriam; Zimprich, Daniel

2008-03-01

Typical Intellectual Engagement (TIE) comprises the preference to engage in cognitively demanding activities and has been proposed as a potential explanatory variable of individual differences in cognitive abilities. Little is known, however, about the factorial structure of TIE, its relations to socio-demographic variables, and its influence on intellectual functioning in old age. In the present study, data of 364 adults (65-81 years) from the Zurich Longitudinal Study on Cognitive Aging (ZULU) were used to investigate the factorial structure of TIE and to examine the hypothesis that TIE is associated more strongly with crystallized intelligence than with fluid intelligence in old age. A measurement model of a second order factor based on a structure of four correlated first order factors (Reading, Problem Solving, Abstract Thinking, and Intellectual Curiosity) evinced an excellent fit. After controlling for age, sex, and formal education, TIE was more strongly associated with crystallized intelligence than with fluid intelligence, comparable to results in younger persons. More detailed analyses showed that this association is mostly defined via Reading and Intellectual Curiosity.

Low temperature structural transformation in T[Ni(CN){sub 4}].xpyz with x=1,2; T=Mn,Co,Ni,Zn,Cd; pyz=pyrazine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriguez-Hernandez, J.; Instituto de Ciencia y Tecnologia de Materiales, Universidad de La Habana; Lemus-Santana, A.A.

2010-01-15

The materials under study are pillared solids T[Ni(CN){sub 4}].xpyz with one and two (x=1,2) pyrazine (pyz) molecules and where T=Mn, Co, Ni, Zn, Cd. Stimulated by their structural features and potential role as prototype of porous solids for hydrogen storage, the structural stability under cryogenic conditions for this series of pillared solids was studied. At low temperature, in the 100-200 K range, the occurrence of a reversible structural transformation was found. For T=Mn, Co, Zn, Cd, with x=2, the structural transformation was observed to occur around 185 K, and the low temperature phase crystallizes with a monoclinic unit cell (spacemore » group Pc). This structure change results from certain charge redistribution on cooling within the involved ligands. For T=Ni with x=1, both the low and high temperature phases crystallize with unit cells of tetragonal symmetry, within the same space group but with a different unit cell volume. In this case the structure change is observed around 120 K. Above that temperature the rotational states for the pyrazine molecule are thermally excited and all the pyrazine molecules in the structure become equivalent. Under this condition the material structure is described using a smaller structural unit. The structural study using X-ray powder diffraction data was complemented with calorimetric and Raman spectroscopy measurements. For the low temperature phases the crystal structures were solved from Patterson methods and then refined using the Rietveld method. - Graphical abstract: Low temperature ordered structure for pyrazine in T[Ni(CN){sub 4}].pyz.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barahona, P., E-mail: pbaraho@ucm.cl; Galdámez, A., E-mail: agaldamez@uchile.cl; López-Vergara, F.

CuTi{sub 2−x}M{sub x}S{sub 4} (M=Fe, Mn, Co; x=0.3, 0.5) and CuCr{sub 2−x}Ti{sub x}Se{sub 4} (x=0.3, 0.5, 0.7) chalcospinels were synthesized by conventional solid-state reactions. Their crystal structures were determined by single-crystal X-ray diffraction. All of the phases crystallized in cubic spinel-type structures (space group, Fd3{sup ¯}m). For all of the chalcospinel compounds, the edge-length distortion parameter (ELD) indicated that the most distorted polyhedron was Q[(Ti,M){sub 3}Cu], which displayed an ∼8% distortion from an ideal tetrahedron structure (Q=S or Se). The Mn-based thiospinel CuMn{sub 0.3}Ti{sub 1.7}S{sub 4} is paramagnetic, whereas the Fe-based thiospinels (CuTi{sub 2−x}Fe{sub x}S{sub 4}; x=0.3 and 0.7) aremore » strongly antiferromagnetic due to their spin-glass states. The magnetic susceptibility measurements indicated ferromagnetic behavior for the selenospinels (CuCr{sub 2−x}Ti{sub x}Se{sub 4}; x=0.3, 0.5 and 0.7). - Graphical abstract: View along [1 0 0] of CuCr{sub 2−x}Ti{sub x}Se{sub 4} crystal structure showing tetrahedral and octahedral units. To the right, experimental X-ray powder diffraction pattern of CuCr{sub 1.7}Ti{sub 0.3}Se{sub 4} (top) in compared (in a like-mirror representation) to a simulated X-ray pattern from single-crystal data (bottom). - Highlights: • Chalcogenides belong to the family of compounds spinel-type. • Resolved single crystals of the solid solutions have space group Fd-3m. • The distortion of the tetrahedral and octahedral volume were calculated. • These solid solutions shows a ferromagnetic or spin-glass behavior.« less

Affinity maturation of a portable Fab–RNA module for chaperone-assisted RNA crystallography

PubMed Central

Koirala, Deepak; Shelke, Sandip A; Dupont, Marcel; Ruiz, Stormy; DasGupta, Saurja; Bailey, Lucas J; Benner, Steven A; Piccirilli, Joseph A

2018-01-01

Abstract Antibody fragments such as Fabs possess properties that can enhance protein and RNA crystallization and therefore can facilitate macromolecular structure determination. In particular, Fab BL3–6 binds to an AAACA RNA pentaloop closed by a GC pair with ∼100 nM affinity. The Fab and hairpin have served as a portable module for RNA crystallization. The potential for general application make it desirable to adjust the properties of this crystallization module in a manner that facilitates its use for RNA structure determination, such as ease of purification, surface entropy or binding affinity. In this work, we used both in vitro RNA selection and phage display selection to alter the epitope and paratope sides of the binding interface, respectively, for improved binding affinity. We identified a 5′-GNGACCC-3′ consensus motif in the RNA and S97N mutation in complimentarity determining region L3 of the Fab that independently impart about an order of magnitude improvement in affinity, resulting from new hydrogen bonding interactions. Using a model RNA, these modifications facilitated crystallization under a wider range of conditions and improved diffraction. The improved features of the Fab–RNA module may facilitate its use as an affinity tag for RNA purification and imaging and as a chaperone for RNA crystallography. PMID:29309709

Development of Nanostructured Water Treatment Membranes Based on Thermotropic Liquid Crystals: Molecular Design of Sub‐Nanoporous Materials

PubMed Central

Ogawa, Takafumi; Nakatsuji, Koji; Mitani, Masato; Soberats, Bartolome; Kawata, Ken; Yoshio, Masafumi; Tomioka, Hiroki; Sasaki, Takao; Kimura, Masahiro

2017-01-01

Abstract Supply of safe fresh water is currently one of the most important global issues. Membranes technologies are essential to treat water efficiently with low costs and energy consumption. Here, the development of self‐organized nanostructured water treatment membranes based on ionic liquid crystals composed of ammonium, imidazolium, and pyridinium moieties is reported. Membranes with preserved 1D or 3D self‐organized sub‐nanopores are obtained by photopolymerization of ionic columnar or bicontinuous cubic liquid crystals. These membranes show salt rejection ability, ion selectivity, and excellent water permeability. The relationships between the structures and the transport properties of water molecules and ionic solutes in the sub‐nanopores in the membranes are examined by molecular dynamics simulations. The results suggest that the volume of vacant space in the nanochannel greatly affects the water and ion permeability. PMID:29375969

Structural characterization, surface characteristics and non covalent interactions of a heterocyclic Schiff base: Evaluation of antioxidant potential by UV-visible spectroscopy and DFT

NASA Astrophysics Data System (ADS)

Chithiraikumar, S.; Gandhimathi, S.; Neelakantan, M. A.

2017-06-01

A heterocyclic Schiff base, (E)-4-(1-((pyridin-2-ylmethyl)imino)ethyl)benzene-1,3-diol (L) was synthesized and isolated as single crystals. Its structure was characterized by FT-IR, UV, 1H and 13C NMR, and further confirmed by X-ray crystallography. Qualitatively and quantitatively the various interactions in the crystal structure of L has been analyzed by Hirshfeld surfaces and 2D fingerprint plots. Non covalent interactions have been studied by electron localization function (ELF) and mapped with reduced density gradient (RDG) analysis. The molecular structure was studied computationally by DFT-B3LYP/6-311G(d,p) calculations. HOMO-LUMO energy levels, chemical reactivity descriptors and thermodynamic parameters have been investigated at the same level of theory. The antioxidant potential of L was evaluated experimentally by measuring DPPH free radical scavenging effect using UV-visible spectroscopy and theoretically by DFT. Theoretical parameters, such as bond dissociation enthalpy (BDE) and spin density calculated suggests that antioxidant potential of L is due to H atom abstraction from the sbnd OH group.

Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Popa, Karin; Raison, Philippe E., E-mail: philippe.raison@ec.europa.eu; Martel, Laura

2015-10-15

PuPO{sub 4} was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β{sup −} decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state {sup 31}P NMR agrees with the XANES results and the presence of a solid-solution. - Graphical abstract: A full structural analysis of PuPO{sub 4} based on Rietveld analysis ofmore » room temperature X-ray diffraction data, XANES and MAS NMR measurements was performed. - Highlights: • The crystal structure of PuPO{sub 4} monazite is solved. • In PuPO{sub 4} plutonium is strictly trivalent. • The presence of a minute amount of Am{sup III} is highlighted. • We propose PuPO{sub 4} as a potential reference material for spectroscopic and microscopic studies.« less

Ce{sub 2}PdIn{sub 8}, Ce{sub 3}PdIn{sub 11} and Ce{sub 5}Pd{sub 2}In{sub 19}—members of homological series based on AuCu{sub 3}- and PtHg{sub 2}-type structural units

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tursina, A.; Nesterenko, S.; Seropegin, Y.

Crystal structures of three members of a unique homological series with the general formula Ce{sub m}Pd{sub n}In{sub 3m+2n} based on the AuCu{sub 3} and PtHg{sub 2} structure types were studied by single-crystal X-ray diffraction. The compounds crystallize with space group P4/mmm (Z=1) and the lattice parameters: a=4.6900(9) Å, c=12.185(6) Å for Ce{sub 2}PdIn{sub 8}, a=4.6846(8) Å, c=16.846(8) Å for Ce{sub 3}PdIn{sub 11}, and a=4.70120(10) Å, c=29.1359(4) Å for Ce{sub 5}Pd{sub 2}In{sub 19}. The crystal structures of Ce{sub 3}PdIn{sub 11} and Ce{sub 5}Pd{sub 2}In{sub 19} represent new types. The three structures constitute of [CeIn{sub 3}] cuboctahedra layers and [PdIn{sub 2}] rectangularmore » polyhedra layers, alternating along the tetragonal c-axis in accordance with the m:n proportion. The magnetic and electrical transport properties of the novel compounds Ce{sub 3}PdIn{sub 11} and Ce{sub 5}Pd{sub 2}In{sub 19} were investigated down to 1.72 K. Both indides are Curie–Weiss paramagnets due to the presence of fairly well localized 4f electrons of trivalent cerium ions. The electrical resistivity of both materials is dominated over an extended temperature range by strong spin–flip Kondo interactions with the characteristic temperature scale of 20–30 K. - Graphical abstract: TOC Figure Crystal structures of Ce{sub 3}PdIn{sub 11}, Ce{sub 2}PdIn{sub 8}, and Ce{sub 5}Pd{sub 2}In{sub 19}. Highlights: ► Large section of Ce–Pd–In phase diagram was examined. ► Three distinct ternary phases were identified, two of them for the first time. ► Crystal structures of two novel compounds constitute new structure types. ► The determined crystal structures show close mutual relationship. ► Ce{sub 3}PdIn{sub 11} and Ce{sub 5}Pd{sub 2}In{sub 19} are paramagnetic Kondo lattices.« less

Crystal structure of cbbF from Zymomonas mobilis and its functional implication

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, Hyo-Jeong; Park, Suk-Youl; Kim, Jeong-Sun, E-mail: jsunkim@chonnam.ac.kr

2014-02-28

Highlights: • The crystal structure of one cbbF from Zymomonas mobilis was revealed. • Scores of residues form two secondary structures with a non-polar protruded residue. • It exists as a dimeric form in solution. - Abstract: A phosphate group at the C1-atom of inositol-monophosphate (IMP) and fructose-1,6-bisphosphate (FBP) is hydrolyzed by a phosphatase IMPase and FBPase in a metal-dependent way, respectively. The two enzymes are almost indiscernible from each other because of their highly similar sequences and structures. Metal ions are bound to residues on the β1- and β2-strands and one mobile loop. However, FBP has another phosphate andmore » FBPases exist as a higher oligomeric state, which may discriminate FBPases from IMPases. There are three genes annotated as FBPases in Zymomonas mobilis, termed also cbbF (ZmcbbF). The revealed crystal structure of one ZmcbbF shows a globular structure formed by five stacked layers. Twenty-five residues in the middle of the sequence form an α-helix and a β-strand, which occupy one side of the catalytic site. A non-polar Leu residue among them is protruded to the active site, pointing out unfavorable access of a bulky charged group to this side. In vitro assays have shown its dimeric form in solution. Interestingly, two β-strands of β1 and β2 are disordered in the ZmcbbF structure. These data indicate that ZmcbbF might structurally belong to IMPase, and imply that its active site would be reorganized in a yet unreported way.« less

Crystal structure of cathepsin A, a novel target for the treatment of cardiovascular diseases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schreuder, Herman A., E-mail: herman.schreuder@sanofi.com; Liesum, Alexander, E-mail: alexander.liesum@sanofi.com; Kroll, Katja, E-mail: katja.kroll@sanofi.com

2014-03-07

Graphical abstract: - Highlights: • The structures of active cathepsin A and the inactive precursor are very similar. • The only major difference is the absence of a 40 residue activation domain. • The termini of the active catalytic core are held together by a disulfide bond. • Compound 1 reacts with the catalytic Ser150, building a tetrahedral intermediate. • Compound 2 is cleaved by the enzyme and a fragment remained bound. - Abstract: The lysosomal serine carboxypeptidase cathepsin A is involved in the breakdown of peptide hormones like endothelin and bradykinin. Recent pharmacological studies with cathepsin A inhibitors inmore » rodents showed a remarkable reduction in cardiac hypertrophy and atrial fibrillation, making cathepsin A a promising target for the treatment of heart failure. Here we describe the crystal structures of activated cathepsin A without inhibitor and with two compounds that mimic the tetrahedral intermediate and the reaction product, respectively. The structure of activated cathepsin A turned out to be very similar to the structure of the inactive precursor. The only difference was the removal of a 40 residue activation domain, partially due to proteolytic removal of the activation peptide, and partially by an order–disorder transition of the peptides flanking the removed activation peptide. The termini of the catalytic core are held together by the Cys253–Cys303 disulfide bond, just before and after the activation domain. One of the compounds we soaked in our crystals reacted covalently with the catalytic Ser150 and formed a tetrahedral intermediate. The other compound got cleaved by the enzyme and a fragment, resembling one of the natural reaction products, was found in the active site. These studies establish cathepsin A as a classical serine proteinase with a well-defined oxyanion hole. The carboxylate group of the cleavage product is bound by a hydrogen-bonding network involving one aspartate and two glutamate side chains. This network can only form if at least half of the carboxylate groups involved are protonated, which explains the acidic pH optimum of the enzyme.« less

Fabrication of one-dimensional alumina photonic crystals by anodization using a modified pulse-voltage method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Shou-Yi; Wang, Jian, E-mail: wangjian@nwnu.edu.cn; Wang, Gang

2015-08-15

Highlights: • The alumina multilayer structure with alternating high and low refractive index is fabricated. • This multilayer shows a strong photonic band gap (PBG) and vivid film colors. • The first PBG could be modulated easily by varying the duration time of constant high or low voltages. • Fabrication of the photonic crystal is obtained by directly electrochemical anodization. • The formation mechanism of multilayer is also discussed. - Abstract: The alumina nanolayer structure with alternating high and low porosities is conveniently fabricated by applying a modified pulse voltage waveform with constant high and low voltage. This structure showsmore » the well-defined layer in a long-range structural periodicity leads to a strong photonic band gap (PBG) from visible to near infrared and brilliant film colors. Compared with the previous reported tuning method, this method is more simple and flexible in tuning the PBG of photonic crystals (PCs). The effect of duration time of high, low and 0 V voltages on PBG is discussed. The first PBG could be modulated easily from the visible to near infrared region by varying the duration time of constant high or low voltages. It is also found that the 0 V lasting for appropriate time is helpful to improve the quality of the PCs. The formation mechanism of multilayer is also discussed.« less

Anharmonic Normal Mode Analysis of Elastic Network Model Improves the Modeling of Atomic Fluctuations in Protein Crystal Structures

PubMed Central

Zheng, Wenjun

2010-01-01

Abstract Protein conformational dynamics, despite its significant anharmonicity, has been widely explored by normal mode analysis (NMA) based on atomic or coarse-grained potential functions. To account for the anharmonic aspects of protein dynamics, this study proposes, and has performed, an anharmonic NMA (ANMA) based on the Cα-only elastic network models, which assume elastic interactions between pairs of residues whose Cα atoms or heavy atoms are within a cutoff distance. The key step of ANMA is to sample an anharmonic potential function along the directions of eigenvectors of the lowest normal modes to determine the mean-squared fluctuations along these directions. ANMA was evaluated based on the modeling of anisotropic displacement parameters (ADPs) from a list of 83 high-resolution protein crystal structures. Significant improvement was found in the modeling of ADPs by ANMA compared with standard NMA. Further improvement in the modeling of ADPs is attained if the interactions between a protein and its crystalline environment are taken into account. In addition, this study has determined the optimal cutoff distances for ADP modeling based on elastic network models, and these agree well with the peaks of the statistical distributions of distances between Cα atoms or heavy atoms derived from a large set of protein crystal structures. PMID:20550915

Structure-Kinetics Correlations in Isostructural Crystals of α-(ortho-Tolyl)-acetophenones: Pinning Down Electronic Effects Using Laser-Flash Photolysis in the Solid State.

PubMed

Ayitou, Anoklase J-L; Flynn, Kristen; Jockusch, Steffen; Khan, Saeed I; Garcia-Garibay, Miguel A

2016-03-02

Aqueous suspensions of nanocrystals in the 200-500 nm size range of isostructural α-(ortho-tolyl)-acetophenone (1a) and α-(ortho-tolyl)-para-methylacetophenone (1b) displayed good absorption characteristics for flash photolysis experiments in a flow system, with transient spectra and decay kinetics with a quality that is similar to that recorded in solution. In contrast to solution measurements, reactions in the solid state were characterized by a rate limiting hydrogen transfer reaction from the triplet excited state and a very short-lived biradical intermediate, which does not accumulate. Notably, the rate for δ-hydrogen atom transfer of 1a (2.7 × 10(7) s(-1)) in the crystalline phase is 18-fold larger than that of 1b (1.5 × 10(6) s(-1)). With nearly identical molecular and crystal structures, this decrease in the rate of δ-hydrogen abstraction can be assigned unambiguously to an electronic effect by the para-methyl group in 1b, which increases the contribution of the (3)π,π* configuration relative to the reactive (3)n,π* configuration in the lowest triplet excited state. These results highlight the potential of relating single crystal X-ray structural data with absolute kinetics from laser flash photolysis.

Synthesis, crystal structure, Hirshfeld surface analysis, spectroscopic characterization, reactivity study by DFT and MD approaches and molecular docking study of a novel chalcone derivative

NASA Astrophysics Data System (ADS)

Arshad, Suhana; Pillai, Renjith Raveendran; Zainuri, Dian Alwani; Khalib, Nuridayanti Che; Razak, Ibrahim Abdul; Armaković, Stevan; Armaković, Sanja J.; Panicker, C. Yohannan; Van Alsenoy, C.

2017-05-01

In the present study, the title compound named as (E)-1-(4-bromophenyl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one was synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in monoclinic crystal system in P21/c space group, unit cell parameters a = 16.7629 (12) Å, b = 13.9681 (10) Å, c = 5.8740 (4) Å, β = 96.3860 (12)° and Z = 4. Hirshfeld surface analysis revealed that the molecular structure is dominated by H⋯H, C⋯H/H⋯C, Br⋯F/F⋯Br and F⋯F contacts. The FT-IR spectrum was recorded and interpreted in details with the aid of Density Functional Theory (DFT) calculations and Potential Energy Distribution (PED) analysis. Average local ionization energies (ALIE) and Fukui functions have been used as quantum-molecular descriptors to locate the molecule sites that could be of importance from the aspect of reactivity. Degradation properties have been assessed by calculations of bond dissociation energies (BDE) for hydrogen abstraction and the rest of the single acyclic bonds, while molecular dynamics (MD) simulations were used in order to calculate radial distribution functions and determine the atoms with significant interactions with water. In order to understand how the title molecule inhibits and hence increases the catalytic efficiency of MOA-B enzyme, molecular docking study was performed.

Pseudosymmetric features of non-centrosymmetric AB type crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gazhulina, A.P., E-mail: asyagazhulina@yandex.ru; Marychev, M.O.

2016-07-15

This work is supplement to our previous investigation (Gazhulina and Marychev, 2015) [1]. We have considered pseudosymmetric features with respect to the operation of inversion (pseudoinversion) for 340 non-centrosymmetric AB type crystals. Analysis of the features of particular structure types allowed us to determine the positions of pseudoinversion centers, subdivide them into separate types, and classify the entire set of crystals studied with respect to the types of pseudoinversion centers and peculiarities of the behavior of the degree of pseudoinversion depending on the ratio of atomic numbers of A and B components. For each group of crystals, average values andmore » lower boundaries of the maximum pseudoinversion are determined and distribution with respect to the degree of pseudoinversion is constructed. - Graphical abstract: A group of 340 non-centrosymmetric AB type crystals have been considered for their pseudosymmetry features with respect to the operation of inversion. Positions of pseudoinversion centers, subdivision of them into separate types, classification of the entire set of crystals studied with respect to the types of pseudoinversion centers and peculiarities of the behavior of the degree of pseudoinversion are established and discussed. Display Omitted - Highlights: • We consider pseudoinversion of 340 non-centrosymmetric AB type crystals. • AB type crystals are divided into three groups with respect to pseudoinversion. • Positions and types of pseudoinversion centers are determined. • Lower boundaries of the maximum pseudoinversion are determined.« less

Crystal structure of product-bound complex of UDP-N-acetyl-D-mannosamine dehydrogenase from Pyrococcus horikoshii OT3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pampa, K.J., E-mail: sagarikakj@gmail.com; Lokanath, N.K.; Girish, T.U.

Highlights: • Determined the structure of UDP-D-ManNAcADH to a resolution of 1.55 Å. • First complex structure of PhUDP-D-ManNAcADH with UDP-D-ManMAcA. • The monomeric structure consists of three distinct domains. • Cys258 acting as catalytic nucleophilic and Lys204 acts as acid/base catalyst. • Oligomeric state plays an important role for the catalytic function. - Abstract: UDP-N-acetyl-D-mannosamine dehydrogenase (UDP-D-ManNAcDH) belongs to UDP-glucose/GDP-mannose dehydrogenase family and catalyzes Uridine-diphospho-N-acetyl-D-mannosamine (UDP-D-ManNAc) to Uridine-diphospho-N-acetyl-D-mannosaminuronic acid (UDP-D-ManNAcA) through twofold oxidation of NAD{sup +}. In order to reveal the structural features of the Pyrococcus horikoshii UDP-D-ManNAcADH, we have determined the crystal structure of the product-bound enzyme bymore » X-ray diffraction to resolution of 1.55 Å. The protomer folds into three distinct domains; nucleotide binding domain (NBD), substrate binding domain (SBD) and oligomerization domain (OD, involved in the dimerization). The clear electron density of the UDP-D-ManNAcA is observed and the residues binding are identified for the first time. Crystal structures reveal a tight dimeric polymer chains with product-bound in all the structures. The catalytic residues Cys258 and Lys204 are conserved. The Cys258 acts as catalytic nucleophile and Lys204 as acid/base catalyst. The product is directly interacts with residues Arg211, Thr249, Arg244, Gly255, Arg289, Lys319 and Arg398. In addition, the structural parameters responsible for thermostability and oligomerization of the three dimensional structure are analyzed.« less

The effect of Eu{sup 2+} doping concentration on luminescence properties of Sr{sub 3}B{sub 2}O{sub 6}:Eu{sup 2+} yellow phosphor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Yue; Liu, Quansheng, E-mail: liuqs@cust.edu.cn; School of Physics, JiLin University, No. 2699 Qianjin Street, Changchun 130012

2013-10-15

Graphical abstract: - Highlights: • The concentration quenching mechanism of Sr{sub 3}B{sub 2}O{sub 6}:Eu{sup 2+}can be interpreted by the dipole–dipole (d–d) interaction of Eu{sup 2+} ions. • The average electronegativity of O{sup 2−} ions located around Eu{sup 2+} ion is 1.9991 eV. • The optimum concentration of Eu{sup 2+} ions in Sr{sub 3}B{sub 2}O{sub 6} is 7 mol%. • Sr{sub 3}B{sub 2}O{sub 6}:Eu{sup 2+} is a hexagonal crystal structure. - Abstract: The Sr{sub 3}B{sub 2}O{sub 6}:Eu{sup 2+} yellow phosphors were synthesized by high-temperature solid state reaction method. The crystal structure and optical properties of the Sr{sub 3}B{sub 2}O{sub 6}:Eu{sup 2+}more » phosphor was studied. Results indicate that Sr{sub 3}B{sub 2}O{sub 6}:Eu{sup 2+} has a hexagonal crystal structure. The excitation spectrum indicates that this phosphor can be effectively excited by ultraviolet light of near 390 nm and blue light of 460 nm. The emission spectrum shows a intense broad band spectrum peaking at 566 nm, which corresponds to the 4f{sup 6}({sup 7}F)5d ({sup 2}e{sub g})→{sup 8}S{sub 7/2} (4f{sup 7})transition of Eu{sup 2+} ion. The excitation spectrum is a broad asymmetric excitation band extending from 300 nm to 500 nm and the main excitation peak is at 468 nm. The average electronegativity of O{sup 2−} ions located around Eu{sup 2+} ion is 1.9991 eV. The optimum concentration of Eu{sup 2+} is 7 mol%. The concentration quenching mechanism can be interpreted by the dipole–dipole (d–d) interaction of Eu{sup 2+} ions.« less

Synthesis, crystal structure and optical properties of a novel sodium lead pentaborate, NaPbB{sub 5}O{sub 9}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Min; Graduate University of Chinese Academy of Sciences, Beijing 100049; Pan, Shilie, E-mail: slpan@ms.xjb.ac.c

A novel sodium lead pentaborate, NaPbB{sub 5}O{sub 9}, has been successfully synthesized by standard solid-state reaction. The single-crystal X-ray structural analysis showed that NaPbB{sub 5}O{sub 9} crystallizes in the monoclinic space group P2{sub 1}/c with a=6.5324(10) A, b=13.0234(2) A, c=8.5838(10) A, {beta}=104.971(10){sup o}, and Z=4. The crystal structure is composed of double ring [B{sub 5}O{sub 9}]{sup 3-} units, [PbO{sub 7}] and [NaO{sub 7}] polyhedra. [B{sub 5}O{sub 9}]{sup 3-} groups connect with each other forming two-dimensional infinite {sub {infinity}}[B{sub 5}O{sub 9}]{sup 3-} layers, while [PbO{sub 7}] and [NaO{sub 7}] polyhedra are located between the layers. [PbO{sub 7}] polyhedra linked together viamore » corner-sharing O atom forming novel infinite {sub {infinity}}[PbO{sub 6}] chains along the c axis. The thermal behavior, IR spectrum and the optical diffuse reflectance spectrum of NaPbB{sub 5}O{sub 9} were reported. -- Graphical abstract: A new phase, NaPbB{sub 5}O{sub 9}, has been discovered in the ternary M{sub 2}O-PbO-B{sub 2}O{sub 3} (M=alkali-metal) system. The crystal structure consists of a novel infinite {sub {infinity}}[PbO{sub 6}] chains. Display Omitted Research highlights: NaPbB{sub 5}O{sub 9} is the first borate discovered in the ternary M{sub 2}O-PbO-B{sub 2}O{sub 3} (M=alkali-metal) system. NaPbB{sub 5}O{sub 9} crystal structure includes a two-dimensional infinite {sub {infinity}}[B{sub 5}O{sub 9}]{sup 3-} layers and a novel one-dimensional infinite {sub {infinity}}[PbO{sub 6}] chains. [PbO{sub 7}] polyhedron has a highly asymmetric bonding configuration.« less

Novel Epitaxy Between Oxides and Semiconductors - Growth and Interfacial Structures

DTIC Science & Technology

2007-05-16

observed to be impressively good. 15. SUBJECT TERMS Nanotechnology, Gallium Nitride 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT Same as...with precursors or gases, a high-purity sapphire was employed in this work. E-beam evaporation was used due to the high melting point of sapphire, and...were carried out on a four-circle triple -axes diffractometer, using a 12 kW rotating anode Cu K-alpha source. A pair of graphite crystals is used to

Surfactant-assisted synthesis of mono-dispersed cubic BaTiO{sub 3} nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hai, Chunxi; Inukai, Koji; Takahashi, Yosuke

2014-09-15

Mono-dispersed BaTiO{sub 3} nanoparticles have been prepared via the assistance of capping agent poly(vinylpyrrolidone) (PVP). - Highlights: • BaTiO{sub 3} nanoparticles with single cubic crystal structure. • Poor dispersibility of nanoparticles has been overcome by in situ modification way. • Growth competition between BaTiO3 core and polymer shell. - Abstract: In this study, poly(vinylpyrrolidone)-assisted synthesis of mono-dispersed BaTiO{sub 3} nanoparticles have been reported. The various processing parameters, namely, refluxing temperature, KOH concentration, and poly(vinylpyrrolidone) concentration, have been varied, and the effects on the growth of BaTiO{sub 3} particles have been analyzed systematically. X-ray diffraction studies indicated that poly(vinylpyrrolidone) did notmore » affect the crystal structure, but rather influenced the crystal lattice structure. In addition, the use of surfactant poly(vinylpyrrolidone) hindered the agglomeration of the nanoparticles, and facilitated the formation of mono-dispersed core–shell organic/inorganic hybrid nanocomposite. Furthermore, the mineralizer KOH promoted the dissolution of reactants and promoted the crystallization of BaTiO{sub 3} particles. Accordingly, the dissolution-precipitation scheme was believed to be the mechanism underlying the formation of BaTiO{sub 3} particles. This was further substantiated by the experimental observations, which indicated that the nucleation and crystallization of the particles was affected by the KOH concentration in the reaction system. Finally, the formation of mono-dispersed core–shell nanocomposites proceeded via reaction limited cluster aggregation. We believe that the method proposed in this study could be extended for the synthesis of mono-dispersed nanoparticles for industrial applications.« less

Synthesis and anisotropic properties of single crystalline Ln{sub 2}Ru{sub 3}Al{sub 15+x} (Ln=Gd, Tb)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morrison, Gregory; Prestigiacomo, Joseph; Haldolaarachchige, Neel

2016-04-15

Single crystals of Ln{sub 2}Ru{sub 3}Al{sub 15+x} (Ln=Gd, Tb) have been grown using the self-flux method under Ru-poor conditions. The structure of the Gd analog is found to be highly dependent on the synthesis method. Gd{sub 2}Ru{sub 3}Al{sub 15.08} orders antiferromagnetically at 17.5 K. Tb{sub 2}Ru{sub 3}Al{sub 15.05} enters an antiferromagnetic state at 16.6 K followed by a likely incommensurate-to-commensurate transition at 14.9 K for crystals oriented with H//ab. For crystals oriented with H//c, a broad maximum is observed in the temperature dependent M/H, indicative of a highly anisotropic magnetic system with the hard axis in the c-direction. The magnetizationmore » as a function of field and magnetoresistance along the ab-direction of Tb{sub 2}Ru{sub 3}Al{sub 15.05} display a stepwise behavior and indicate strong crystalline electric field effects. - Graphical abstract: Single crystal, structure, and highly anisotropic magnetoresistance due to strong crystalline electric field effects of Tb{sub 2}Ru{sub 3}Al{sub 15.05}. - Highlights: • Single crystals of Ln{sub 2}Ru{sub 3}Al{sub 15+x} were grown for the first time via flux growth. • The structure of Gd{sub 2}Ru{sub 3}Al{sub 15.09} differs from that of arc melted Gd{sub 2}Ru{sub 3.08}Al{sub 15}. • Tb{sub 2}Ru{sub 3}Al{sub 15.05} exhibits highly anisotropic magnetic and transport properties. • The properties of Tb{sub 2}Ru{sub 3}Al{sub 15.05} arise due to crystalline electric field effects.« less

Zinc(II) and Cadmium(II) coordination polymers constructed from phenylenediacetate ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sezer, Güneş Günay; Department of Chemistry, Eskişehir Osmangazi University, Eskişehir; Yeşilel, Okan Zafer

ABSTRACT: A series of new coordination polymers {[Zn(μ-opda)(μ-bpa)]·2H_2O}{sub n} (1), [Zn(μ{sub 3}-ppda)(μ-bpa)]{sub n} (2), [Cd(μ{sub 3}-ppda)(μ-bpa)]{sub n} (3), [Cd(μ{sub 3}-mpda)(μ-bpa)]{sub n} (4) and [Cd(μ{sub 3}-mpda)(μ-bipy)]{sub n} (5), (o/m/ppda=1,2/1,3/1,4-phenylenediacetate, bpa=1,2-bi(4-pyridyl)ethane, bipy=4,4′-bipyridine) were synthesized. Their structures were characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffraction. Furthermore, the effect of metal sources (zinc acetate and zinc oxide) and acidity of the solution on the structure of the coordination polymers was discussed for complexes 1 and 5, respectively. The single-crystal X-ray crystallographic studies revealed that complexes 1, 3, 4 and 5 are uninodal (4)-connected 2D frameworks and display sql topology withmore » the point symbol of (4{sup 4}.6{sup 2}). Complex 2 is 3D coordination polymer and exhibits pcu topology with the point symbol of (4{sup 12}.6{sup 3}). In addition, the luminescent properties and thermal behavior of all complexes were also investigated. - Graphical abstract: Scheme 1. Topologies of Coordination Polymers Reported in This Paper.« less

Innovative methodology for the synthesis of Ba-M hexaferrite BaFe{sub 12}O{sub 19} nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmed, M.A., E-mail: moala@47hotmail.com; Helmy, N.; El-Dek, S.I.

2013-09-01

Graphical abstract: Transmission electron microscope images for the BaFe12O19. - Highlights: • BaFe{sub 12}O{sub 19}nanoparticles were prepared in single-phase from organometallic precursors. • BaFe{sub 12}O{sub 19} possesses small size 65 nm, H{sub C} = 3695 Oe and M{sub s} = 58 emu/g. • This method of preparation could be extended in the synthesis of other metal oxide nanoparticles. - Abstract: In this piece of work, high quality and homogeneity, barium hexaferrite (BaM) BaFe{sub 12}O{sub 19} nanoparticles were prepared from organometallic precursors for the 1st time. This method is based on the formation of supramolecular crystal structure of Ba[Fe(H{sub 3}NCH{sub 2}CH{submore » 2}NH{sub 3})]Cl{sub 7}·8H{sub 2}O. The crystal structure, morphology and magnetic properties of BaFe{sub 12}O{sub 19} at two different annealing temperatures namely 1000 °C and 1200 °C were investigated using X-ray diffraction, transmission electron microscope TEM and vibrating sample magnetometry (VSM). The results show that monophasic nanoparticles of hexaferrites were obtained. Nanoparticles of crystallite size 40–50 nm distinguished by narrow distribution and excellent homogeneity were obtained with superior magnetic properties which suggested single-domain particles of Ba-M hexaferrite.« less

Morphology and structure features of ZnAl{sub 2}O{sub 4} spinel nanoparticles prepared by matrix-isolation-assisted calcination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Xuelian, E-mail: xueliandu@126.com; Li, Liqiang; Zhang, Wenxing

2015-01-15

Graphical abstract: The substrate ZnO as the isolation medium is effective in preventing the sintering and agglomeration of ZnAl{sub 2}O{sub 4} nanoparticles, and it also prevents their contamination. High purity, well-dispersed, and single-crystal ZnAl{sub 2}O{sub 4} nanoparticles with 3.72 eV band gap were obtained. - Abstract: Well-dispersed ZnAl{sub 2}O{sub 4} spinel nanoparticles with an average crystalline size of 25.7 nm were synthesized successfully and easily by polymer-network and matrix-isolation-assisted calcination. The product microstructure and features were investigated by X-ray diffractometry, thermogravimetric and differential thermal analysis, Fourier transform-infrared spectroscopy, N{sub 2} adsorption–desorption isotherms, and energy dispersive X-ray spectra. The morphology andmore » optical performance of the as-prepared ZnAl{sub 2}O{sub 4} nanoparticles were characterized by scanning electron microscope, transmission electron microscopy, and photoluminescence spectrometer. Experimental results indicate that excess ZnO acted as the isolation medium is effective in preventing the sintering and agglomeration of ZnAl{sub 2}O{sub 4} nanoparticles, and it also prevents their contamination. Then, high purity and well-dispersed ZnAl{sub 2}O{sub 4} nanoparticles with single-crystal structure were obtained.« less

A phase width for CaGaSn. Crystal structure of mixed intermetallic Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x} and SmGa{sub x}Sn{sub 3−x}, stability, geometry and electronic structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tillard, Monique, E-mail: mtillard@univ-montp2.fr

X-ray single-crystal structure has been established for new compositions in intermetallic systems of tin and gallium. Crystals were successfully obtained in alloys prepared from elements. The structure of SmGaSn{sub 2} (cubic Pm3̄m, a=4.5778(8) Å, Z=1, R1=0.012) is described with atomic disorder at all Sn/Ga positions and the structure of Ca{sub 4}Ga{sub 4.9}Sn{sub 3.1} (hexagonal, P6{sub 3}/mmc, a=4.2233(9), c=17.601(7) Å, Z=1, R1=0.062) raises an interesting question about existence of a composition domain for CaGaSn. Finally, Ca{sub 4}Ga{sub 4.9}Sn{sub 3.1} should be considered as a particular composition of Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x}, a compound assumed to exist in the range x ~more » 0−1. Partial atomic ordering characterizes the Sn/Ga puckered layers of hexagons whose geometries are analyzed and discussed comparatively with analogous arrangements in AlB{sub 2} related hexagonal compounds. The study is supported by rigid band model and DFT calculations performed for different experimental and hypothetic arrangements. - Graphical abstract: A phase width for Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x} belonging to the hexagonal YPtAs structure-type. - Highlights: • Single crystals of mixed tin gallium ternary intermetallics were obtained. • Partial ordering at metal sites and phase width are evidenced for Ca{sub 4}Ga{sub 4+x}Sn{sub 4−x}. • Layer deviation to flatness is studied comparatively with related structures. • Geometry and stability analyses based on DFT calculations are provided.« less

Crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} and luminescence properties of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 2+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iwata, Tomoyuki; Haniuda, Masahide; Fukuda, Koichiro

2008-01-15

The crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} was determined from laboratory X-ray powder diffraction data (CuK{alpha}{sub 1}) using the Rietveld method, with the anisotropic displacement parameters being assigned for all atoms. The crystal structure is cubic (space group I4-bar 3d, Z=2) with lattice dimensions a=1.200950(5) nm and V=1.73211(1) nm{sup 3}. The reliability indices calculated from the Rietveld method were R{sub wp}=8.48% (S=1.21), R{sub p}=6.05%, R{sub B}=1.27% and R{sub F}=1.01%. The validity of the structural model was verified by the three-dimensional electron density distribution, the structural bias of which was reduced as much as possible using the maximum-entropy methods-basedmore » pattern fitting (MPF). The reliability indices calculated from the MPF were R{sub B}=0.75% and R{sub F}=0.56%. In the structural model there are one Ca site, two Al sites, two O sites and one Cl site. This compound is isomorphous with Ca{sub 12}Al{sub 10.6}Si{sub 3.4}O{sub 32}Cl{sub 5.4}. Europium-doped sample Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2}:Eu{sup 2+} was prepared and the photoluminescence properties were presented. The excitation spectrum consisted of two wide bands, which were located at about 268 and 324 nm. The emission spectrum, when excited at 324 nm, resulted in indigo light with a peak at about 442 nm. - Graphical abstract: A portion of the crystal structure of Ca{sub 12}Al{sub 14}O{sub 32}Cl{sub 2} showing eight-membered AlO{sub 4} rings and Ca-Cl-Ca unit.« less

Non-linear thermal evolution of the crystal structure and phase transitions of LaFeO{sub 3} investigated by high temperature X-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Selbach, Sverre M.; Tolchard, Julian R.; Fossdal, Anita

2012-12-15

The crystal structure, anisotropic thermal expansion and structural phase transition of the perovskite LaFeO{sub 3} has been studied by high-temperature X-ray diffraction from room temperature to 1533 K. The structural evolution of the orthorhombic phase with space group Pbnm and the rhombohedral phase with R3{sup Macron }c structure of LaFeO{sub 3} is reported in terms of lattice parameters, thermal expansion coefficients, atomic positions, octahedral rotations and polyhedral volumes. Non-linear lattice expansion across the antiferromagnetic to paramagnetic transition of LaFeO{sub 3} at T{sub N}=735 K was compared to the corresponding behavior of the ferroelectric antiferromagnet BiFeO{sub 3} to gain insight tomore » the magnetoelectric coupling in BiFeO{sub 3}, which is also multiferroic. The first order phase transition of LaFeO{sub 3} from Pbnm to R3{sup Macron }c was observed at 1228{+-}9 K, and a subsequent transition to Pm3{sup Macron }m was extrapolated to occur at 2140{+-}30 K. The stability of the Pbnm and R3{sup Macron }c polymorphs of LaFeO{sub 3} is discussed in terms of the competing enthalpy and entropy of the two crystal polymorphs and the thermal evolution of the polyhedral volume ratio V{sub A}/V{sub B}. - Graphical abstract: Aniostropic thermal evolution of the lattice parameters and phase transition of LaFeO{sub 3}. Highlights: Black-Right-Pointing-Pointer The crystal structure of LaFeO{sub 3} is studied by HTXRD from RT to 1533 K. Black-Right-Pointing-Pointer A non-linear expansion across the Neel temperature is observed for LaFeO{sub 3}. Black-Right-Pointing-Pointer The ratio V{sub A}/V{sub B} is used to rationalize the thermal evolution of the structure.« less

Crystal structures and compressibility of novel iron borides Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} synthesized at high pressure and high temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bykova, E., E-mail: elena.bykova@uni-bayreuth.de; Laboratory of Crystallography, University of Bayreuth, D-95440 Bayreuth; Gou, H.

2015-10-15

We present here a detailed description of the crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe{sub 2}B{sub 7} (the bulk modulus K{sub 0}= 259(1.8) GPa, K{sub 0}′= 4 (fixed)) is even lower than that of FeB{sub 4} and comparable with that of MnB{sub 4}, known for highmore » bulk moduli among 3d metal borides. Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. Fe{sub x}B{sub 50} does not show considerable anisotropy in the elastic behavior. - Graphical abstract: Crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} (x=1.01(1), 1.04(1), 1.32(1)). - Highlights: • Novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50}, were synthesized under HPHT conditions. • Fe{sub 2}B{sub 7} has a unique orthorhombic structure (space group Pbam). • Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds that results in high bulk modulus. • Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B composed of B{sub 12} icosahedra. • In Fe{sub x}B{sub 50} intraicosahedral bonds are stiffer than intericosahedral ones.« less

ZnTeO{sub 3} crystal growth by a modified Bridgman technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nawash, Jalal M., E-mail: nawashj@uww.edu; Lynn, Kelvin G.

2014-12-15

Highlights: • ZnTeO{sub 3} single crystals were grown for the first time by a modified Bridgman method. • The growth is still possible in a system that lacks congruent melting. • A growth is best when melt is exposed to a steeper axial thermal gradient. • Optical and electrical properties were investigated for the grown crystals. - Abstract: Zinc Tellurite (ZnTeO{sub 3}) crystals were grown for the first time using a modified Bridgman method with a 2.5 kHz radio frequency (RF) furnace. Single crystal growth of ZnTeO{sub 3} was hindered by many complicating factors, such as the evaporation of TeO{submore » 2} above 700 °C and the formation of more than one phase during crystal growth. While there were several successful runs that produced ZnTeO{sub 3} single crystals, it was found that large (≥10 cm{sup 3}) single ZnTeO{sub 3} crystals resulted when the crucible was exposed to a steeper vertical thermal gradient and when the temperature of the melt was raised to at least 860 °C. The results of powder X-ray diffraction (XRD) patterns were in accordance with the X-ray powder diffraction file (PDF) for ZnTeO{sub 3}. Some optical, electrical and structural properties of ZnTeO{sub 3} single crystals were reported in this paper.« less

Synthesis, crystal and electronic structure of the quaternary sulfides Ln{sub 2}CuMS{sub 5} (Ln=La, Ce; M=Sb, Bi)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kussainova, Ardak M.; Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716; Akselrud, Lev G.

2016-01-15

The series of quaternary sulfides with general formula Ln{sub 2}CuMS{sub 5} (Ln=La, Ce; M=Sb, Bi) have been synthesized by solid-state reactions. Three representative members have been structurally characterized by single-crystal X-ray diffraction. La{sub 2}CuSbS{sub 5} crystallizes in a new structure type (space group Ima2 (no. 46), Z=4, a=13.401(2) Å, b=7.592(1) Å, c=7.598(1) Å, V=773.1(3) Å{sup 3}). The bismuth analogs of composition La{sub 2}CuBiS{sub 5} and Ce{sub 2}CuBiS{sub 5} crystallize with the La{sub 2}CuInSe{sub 5} structure type (space group Pnma (no. 62), Z=4). Lattice parameters for La{sub 2}CuBiS{sub 5}: a=11.9213(5) Å, b=3.9967(2) Å, c=17.0537(8) Å, V=812.56(7) Å{sup 3}; lattice parameters formore » Ce{sub 2}CuBiS{sub 5}: a=11.9179(15) Å, b=3.9596(5) Å, c=16.955(2) Å, V=800.13(17) Å{sup 3}). The similarities and the differences between the two structures are discussed. Electronic structure calculations for La{sub 2}CuSbS{sub 5} and La{sub 2}CuBiS{sub 5} are also presented; they suggest semiconducting behavior with energy gaps exceeding 1.7 eV. - Graphical abstract: La{sub 2}CuSbS{sub 5} crystallizes in a new structure type (space group Ima2 (no. 46). Its bismuth analog La{sub 2}CuBiS{sub 5} crystallizes in the La{sub 2}CuInSe{sub 5} structure type (space group Pnma (no. 62)). Z=4, a=11.9213(5) Å, b=3.9967(2) Å, c=17.0536(10) Å, V=813.53(10) Å{sup 3}). The structures are based on rare-earth metal atoms coordinated by S atoms in a trigonal-prismatic and/or square-antiprismatic fashion, Cu-centered tetrahedra, and pnictogen atoms in pyramidal or distorted octahedral coordination. - Highlights: • Ln{sub 2}CuSbS{sub 5} are complex quarternary phases crystallizing in their own structure type. • Ln{sub 2}CuSbS{sub 5} and Ce{sub 2}CuBiS{sub 5} are new compound in the respective ternary phase diagrams. • Ln{sub 2}CuSbS{sub 5} on one side, and Ln{sub 2}CuBiS{sub 5} on the other are not isotypic.« less

Li{sub 2}Sr{sub 4}B{sub 12}O{sub 23}: A new alkali and alkaline-earth metal mixed borate with [B{sub 10}O{sub 18}]{sup 6-} network and isolated [B{sub 2}O{sub 5}]{sup 4-} unit

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Min; Graduate University of Chinese Academy of Sciences, Beijing 100049; Pan Shilie, E-mail: slpan@ms.xjb.ac.cn

2012-06-15

A novel ternary lithium strontium borate Li{sub 2}Sr{sub 4}B{sub 12}O{sub 23} crystal with size up to 20 mm Multiplication-Sign 10 mm Multiplication-Sign 4 mm has been grown via the top-seeded solution growth method below 730 Degree-Sign C. Single-crystal XRD analyses showed that Li{sub 2}Sr{sub 4}B{sub 12}O{sub 23} crystallizes in the monoclinic space group P2{sub 1}/c with a=6.4664(4) A, b=8.4878(4) A, c=15.3337(8) A, {beta}=102.02(3) Degree-Sign , Z=2. The crystal structure is composed of [B{sub 10}O{sub 18}]{sup 6-} network and isolated [B{sub 2}O{sub 5}]{sup 4-} unit. The IR spectrum further confirmed the presence of both BO{sub 3} and BO{sub 4} groups. TG-DSCmore » and Transmission spectrum were reported. Band structures and density of states were calculated. - Graphical abstract: A new phase, Li{sub 2}Sr{sub 4}B{sub 12}O{sub 23}, has been discovered in the ternary M{sub 2}O-M Prime O-B{sub 2}O{sub 3} (M=alkali-metal, M Prime =alkalineearth metal) system. The crystal structure consists of [B{sub 10}O{sub 18}]{sup 6-} network and isolated [B{sub 2}O{sub 5}]{sup 4-} unit. Highlights: Black-Right-Pointing-Pointer Li{sub 2}Sr{sub 4}B{sub 12}O{sub 23} is a a novel borate discovered in the M{sub 2}O-M Prime O-B{sub 2}O{sub 3} (M=alkali-metal, M Prime =alkaline-earth metal) system. Black-Right-Pointing-Pointer Li{sub 2}Sr{sub 4}B{sub 12}O{sub 23} crystal structure has a three-dimensional crystal structure with [B{sub 10}O{sub 18}]{sup 6-} network and isolated [B{sub 2}O{sub 5}]{sup 4-} unit. Black-Right-Pointing-Pointer Sr{sub 1} and Sr{sub 2} are located in two different channels constructed by {sup 3}{sub {infinity}}[B{sub 10}O{sub 18}] network.« less

Structural Basis for Host Membrane Remodeling Induced by Protein 2B of Hepatitis A Virus

PubMed Central

Vives-Adrián, Laia; Garriga, Damià; Buxaderas, Mònica; Fraga, Joana; Pereira, Pedro José Barbosa

2015-01-01

ABSTRACT The complexity of viral RNA synthesis and the numerous participating factors require a mechanism to topologically coordinate and concentrate these multiple viral and cellular components, ensuring a concerted function. Similarly to all other positive-strand RNA viruses, picornaviruses induce rearrangements of host intracellular membranes to create structures that act as functional scaffolds for genome replication. The membrane-targeting proteins 2B and 2C, their precursor 2BC, and protein 3A appear to be primarily involved in membrane remodeling. Little is known about the structure of these proteins and the mechanisms by which they induce massive membrane remodeling. Here we report the crystal structure of the soluble region of hepatitis A virus (HAV) protein 2B, consisting of two domains: a C-terminal helical bundle preceded by an N-terminally curved five-stranded antiparallel β-sheet that displays striking structural similarity to the β-barrel domain of enteroviral 2A proteins. Moreover, the helicoidal arrangement of the protein molecules in the crystal provides a model for 2B-induced host membrane remodeling during HAV infection. IMPORTANCE No structural information is currently available for the 2B protein of any picornavirus despite it being involved in a critical process in viral factory formation: the rearrangement of host intracellular membranes. Here we present the structure of the soluble domain of the 2B protein of hepatitis A virus (HAV). Its arrangement, both in crystals and in solution under physiological conditions, can help to understand its function and sheds some light on the membrane rearrangement process, a putative target of future antiviral drugs. Moreover, this first structure of a picornaviral 2B protein also unveils a closer evolutionary relationship between the hepatovirus and enterovirus genera within the Picornaviridae family. PMID:25589659

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gil, D.M.; Osiry, H.; Pomiro, F.

The hydrogen bond and π-π stacking are two non-covalent interactions able to support cooperative magnetic ordering between paramagnetic centers. This contribution reports the crystal structure and related magnetic properties for VO[Fe(CN){sub 5}NO]·2H{sub 2}O, which has a layered structure. This solid crystallizes with an orthorhombic unit cell, in the Pna2{sub 1} space group, with cell parameters a=14.1804(2), b=10.4935(1), c=7.1722(8) Å and four molecules per unit cell (Z=4). Its crystal structure was solved and refined from powder X-ray diffraction data. Neighboring layers remain linked through a network of hydrogen bonds involving a water molecule coordinated to the axial position for the Vmore » atom and the unbridged axial NO and CN ligands. An uncoordinated water molecule is found forming a triple bridge between these last two ligands and the coordinated water molecule. The magnetic measurements, recorded down to 2 K, shows a ferromagnetic interaction between V atoms located at neighboring layers, with a Curie-Weiss constant of 3.14 K. Such ferromagnetic behavior was interpreted as resulting from a superexchange interaction through the network of strong OH····O{sub H2O}, OH····N{sub CN}, and OH····O{sub NO} hydrogen bonds that connects neighboring layers. The interaction within the layer must be of antiferromagnetic nature and it was detected close to 2 K. - Graphical abstract: Coordination environment for the metals in vanadyl (II) nitroprusside dihydrate. Display Omitted - Highlights: • Crystal structure of vanadyl nitroprusside dehydrate. • Network of hydrogen bonds. • Magnetic interactions through a network of hydrogen bonds. • Layered transition metal nitroprussides.« less

A{sub 5}RE{sub 4}X[TO{sub 4}]{sub 4} crystal growth: Fluoride flux synthesis of Na{sub 5}Ln{sub 4}F[GeO{sub 4}]{sub 4} (Ln=Pr, Nd), the first quaternary germanate oxyfluorides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Latshaw, Allison M.; Wilkins, Branford O.; Morrison, Gregory

Crystals of Na{sub 5}Pr{sub 4}F[GeO{sub 4}]{sub 4} and Na{sub 5}Nd{sub 4}F[GeO{sub 4}]{sub 4} were synthesized using a eutectic sodium fluoride, sodium chloride flux. Both compounds crystallize in the tetragonal space group I-4 with lattice parameters of a=12.1173(4) Å and c=5.6795(2) Å (Pr) and of a=12.0642(17) Å and c=5.6674(11) Å (Nd). The structure of the reported compounds is three-dimensional with face and corner sharing lanthanide polyhedra which edge and corner share with isolated germanium tetrahedra. These novel compositions represent the first example of quaternary germanium containing oxyfluorides. - Graphical abstract: Structural image of the first examples of quaternary germanate oxyfluorides. Displaymore » Omitted - Highlights: • Molten flux growth of crystals of two lanthanide germanate oxyfluorides. • Expansion of the A{sub 5}RE{sub 4}X[TO{sub 4}]{sub 4} family into germanate oxyfluorides. • Synthesis of Na{sub 5}Nd{sub 4}F[GeO{sub 4}]{sub 4} and Na{sub 5}Pr{sub 4}F[GeO{sub 4}]{sub 4}.« less

The intervening removable affinity tag (iRAT) production system facilitates Fv antibody fragment‐mediated crystallography

PubMed Central

Nomura, Yayoi; Sato, Yumi; Suno, Ryoji; Horita, Shoichiro

2016-01-01

Abstract Fv antibody fragments have been used as co‐crystallization partners in structural biology, particularly in membrane protein crystallography. However, there are inherent technical issues associated with the large‐scale production of soluble, functional Fv fragments through conventional methods in various expression systems. To circumvent these problems, we developed a new method, in which a single synthetic polyprotein consisting of a variable light (VL) domain, an intervening removable affinity tag (iRAT), and a variable heavy (VH) domain is expressed by a Gram‐positive bacterial secretion system. This method ensures stoichiometric expression of VL and VH from the monocistronic construct followed by proper folding and assembly of the two variable domains. The iRAT segment can be removed by a site‐specific protease during the purification process to yield tag‐free Fv fragments suitable for crystallization trials. In vitro refolding step is not required to obtain correctly folded Fv fragments. As a proof of concept, we tested the iRAT‐based production of multiple Fv fragments, including a crystallization chaperone for a mammalian membrane protein as well as FDA‐approved therapeutic antibodies. The resulting Fv fragments were functionally active and crystallized in complex with the target proteins. The iRAT system is a reliable, rapid and broadly applicable means of producing milligram quantities of Fv fragments for structural and biochemical studies. PMID:27595817

Effect of synthesis conditions on the nanopowder properties of Ce{sub 0.9}Zr{sub 0.1}O{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zimicz, M.G.; Fabregas, I.O.; Lamas, D.G.

Graphical abstract: . The synthesis of nanocrystalline Ce{sub 0.9}Zr{sub 0.1}O{sub 2} powders via the gel-combustion method, using different fuels, and following either stoichiometric or non-stoichiometric pH-controlled routes is investigated. Research highlights: {yields} All samples exhibited the fluorite-type crystal structure, nanometric average crystallite size and negligible carbon content. {yields} Synthesis conditions strongly affect the average crystallite size, the degree of agglomeration, the specific surface area and the pore volume. {yields} Our results indicate that, by controlling the synthesis conditions it is possible to obtain solids with custom-made morphological properties. -- Abstract: In this work, the synthesis of nanocrystalline Ce{sub 0.9}Zr{sub 0.1}O{submore » 2} powders via the gel-combustion method, using different fuels, and following either stoichiometric or non-stoichiometric pH-controlled routes is investigated. The objective is to evaluate the effect of synthesis conditions on the textural and morphological properties, and the crystal structure of the synthesized materials. The solids were characterized by nitrogen physisorption, Scanning Electron Microscopy (SEM), X-ray powder diffraction (XPD), and Carbon-Hydrogen-Nitrogen Elemental Analysis (CHN). All the powders exhibited nanometric crystallite size, fluorite-type structure and negligible carbon content. Synthesis conditions strongly affect the average crystallite size, the degree of agglomeration, the specific surface area and the pore volume. Our results indicate that, by controlling the synthesis conditions it is possible to obtain solids with custom-made morphological properties.« less

Effect of the synthesis conditions on the electrochemical properties of LiFePO{sub 4} obtained from NH{sub 4}FePO{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prosini, Pier Paolo, E-mail: pierpaolo.prosini@enea.it; Gislon, Paola; Cento, Cinzia

Graphical abstract: - Highlights: • Four different samples of FAP were synthesized by precipitation techniques. • The samples were used as precursors to synthesize electrochemical active LiFePO{sub 4}. • Their morphology, composition, structure and electrochemical performance were studied. • The LiFePO{sub 4} electrochemical performance resulted affected by the preparation method - Abstract: In this paper the morphological, structural and electrochemical properties of crystalline lithium iron phosphate (LiFePO{sub 4}) obtained from ferrous ammonium phosphate (FAP) have been studied. The FAP was obtained following four different processes, namely: (1) homogeneous phase precipitation, (2) heterogeneous phase precipitation from stoichiometric sodium phosphate, (3) heterogeneousmore » phase precipitation from stoichiometric ammonium phosphate, and (4) heterogeneous phase precipitation from over stoichiometric ammonium phosphate. Lithium iron phosphate was prepared by solid state reaction of FAP with lithium hydroxide. In order to evaluate the effect of reaction time and synthesis temperature the LiFePO{sub 4} was prepared varying the heating temperatures (550, 600 and 700 °C) and the reaction times (1 or 2 h). The morphology of the materials was evaluated by scanning electron microscopy while the chemical composition was determined by electron energy loss spectroscopy. X-ray diffraction was used to evaluate phase composition, crystal structure and crystallite size. The so obtained LiFePO{sub 4}'s were fully electrochemical characterized and a correlation was found between the crystal size and the electrochemical performance.« less

The crystal structures of Ni{sub 3+x}Sn{sub 4}Zn and Ni{sub 6+x}Sn{sub 8}Zn and their structural relations to Ni{sub 3+x}Sn{sub 4}, NiSn and Ni{sub 5−δ}ZnSn{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmetterer, Clemens, E-mail: clemens.schmetterer@univie.ac.at; Effenberger, Herta Silvia; Rajamohan, Divakar

2016-06-15

The crystal structures of two new compounds were determined from single-crystal X-ray diffraction measurements: Ni{sub 3+x}Sn{sub 4}Zn, (x~1.35, a=7.110(2) Å, b=4.123(1) Å, c=10.346(3) Å, β=90.23(2)°, space group I2/m, Z=2. R1=0.025, wR2=0.059 for 748 unique reflections, 35 variable parameters) and Ni{sub 6+x}Sn{sub 8}Zn, x~1.35 (a=12.379(3) Å, b=4.095(1) Å, c=12.155(3) Å, β=116.25(3)°, space group C2/m, Z=2. R1=0.026, wR2=0.052 for 1346 unique reflections, 60 variable parameters). In addition, a structural refinement was performed for Ni{sub 3+x}Sn{sub 4}, x~0.13 (a=12.264(3) Å, b=4.066(1) Å, c=5.223(2) Å, β=104.85(3)°, space group C2/m, Z=2. R1=0.019, wR2=0.046 for 617 unique reflections, 29 variable parameters). The three compounds show pronouncedmore » similarities among each other as well as to the crystal structures of surrounding binary Ni–Sn and ternary Ni–Sn–Zn compounds. In particular, the two new compounds form a homologous series with Ni{sub 3+x}Sn{sub 4}, x~0.13. They contain “Ni{sub 4}Sn{sub 4}” and “Ni{sub 2}Sn{sub 4}” building blocks which by different interconnection build up the distinct structures. Topological relations with NiSn and Ni{sub 5−δ}Sn{sub 4}Zn, δ~0.25 are evident. - Graphical abstract: Projection of the structure of Ni{sub 6+x}ZnSn{sub 8}, x~1.35 and constituent building blocks. Display Omitted - Highlights: • The crystal structures of Ni{sub 6+x}Sn{sub 8}Zn and Ni{sub 3+x}Sn{sub 4}Zn were determined using single crystal XRD. • Topological relations to Ni–Sn and Ni–Sn–Zn compounds were established and discussed. • Common structural units were identified and their interconnection patterns described.« less

X-ray structural study of intermetallic alloys RT{sub 2}Si and RTSi{sub 2} (R=rare earth, T=noble metal)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gribanov, Alexander, E-mail: avgri@mail.r; Chemistry Department of the Moscow State University, Leninskie Gory, GSP-1, 119991 Moscow; Grytsiv, Andriy

Two series of intermetallic alloys, RT{sub 2}Si and RTSi{sub 2}, have been synthesized from stoichiometric compositions. The crystal structures of EuPt{sub 1+x}Si{sub 2-x} (CeNiSi{sub 2}-type), CeIr{sub 2}Si (new structure type), YbPd{sub 2}Si and YbPt{sub 2}Si (both YPd{sub 2}Si-type) have been elucidated from X-ray single crystal CCD data, which were confirmed by XPD experiments. The crystal structures of LaRh{sub 2}Si and LaIr{sub 2}Si (CeIr{sub 2}Si-type), {l_brace}La,Ce,Pr,Nd{r_brace}AgSi{sub 2} (all TbFeSi{sub 2}-type), and EuPt{sub 2}Si (inverse CeNiSi{sub 2}-type) were characterized by XPD data. RT{sub 2}Si/RTSi{sub 2} compounds were neither detected in as-cast alloys Sc{sub 25}Pt{sub 50}Si{sub 25}, Eu{sub 25}Os{sub 25}Si{sub 50} and Eu{submore » 25}Rh{sub 25}Si{sub 50} nor after annealing at 900 {sup o}C. Instead, X-ray single crystal data prompted Eu{sub 2}Os{sub 3}Si{sub 5} (Sc{sub 2}Fe{sub 3}Si{sub 5}-type) and EuRh{sub 2+x}Si{sub 2-x} (x=0.04, ThCr{sub 2}Si{sub 2}-type) as well as a new structure type for Sc{sub 2}Pt{sub 3}Si{sub 2} (own type). - Graphical abstract: Two series of the intermetallic compounds, RT{sub 2}Si and RTSi{sub 2}, have been investigated by X-ray diffraction methods. The new tetragonal CeIr{sub 2}Si-type of the crystal structure was described and the interrelation between orthorhombic CeNiSi{sub 2} and tetragonal CeIr{sub 2}Si had been discussed as a similar packing of the BaAl{sub 4} and AlB{sub 2} slabs.« less

Synthesis, structure characterization and optical properties of a new tripotassium cadmium pentaborate, K{sub 3}CdB{sub 5}O{sub 10}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu Hongwei; Graduate school of Chinese Academy of Sciences, Beijing 100049; Pan Shilie, E-mail: slpan@ms.xjb.ac.cn

A new ternary borate oxide, K{sub 3}CdB{sub 5}O{sub 10}, has been synthesized by solid-state reaction at 580 deg. C. The compound crystallizes in the monoclinic space group P2{sub 1}/n with a=7.6707 (7) A, b=19.1765 (17) A, c=7.8784 (6) A, {beta}=115.6083 (49){sup o}, and Z=4. The crystal structure consists of a two-dimensional infinite [CdB{sub 5}O{sub 10}] layer, which forms by connecting isolated double ring [B{sub 5}O{sub 10}] groups and CdO{sub 4} tetrahedra. K atoms filling in the interlayer and intralayer link the layers together and balance charge. The IR spectrum has been studied and confirmed the presence of both BO{sub 3}more » and BO{sub 4} groups, and the UV-vis-IR diffuse reflectance spectrum exhibits a band gap of about 3.4 eV. The DSC analysis proves that K{sub 3}CdB{sub 5}O{sub 10} is a congruent melting compound. - Graphical abstract: A new phase, K{sub 3}CdB{sub 5}O{sub 10}, has been discovered in the ternary K{sub 2}O-CdO-B{sub 2}O{sub 3} system. The crystal structure consists of a two-dimensional infinite [CdB{sub 5}O{sub 10}] layer. Highlights: > The compound, K{sub 3}CdB{sub 5}O{sub 10}, was synthesized and characterized for the first time. {yields}K{sub 3}CdB{sub 5}O{sub 10} is a congruent melting compound, which means the large single crystals could be grown from the melt using the Czochralski pulling method. {yields}The crystal structure consists of a two-dimensional infinite [CdB{sub 5}O{sub 10}].« less

X-ray structural studies and physicochemical characterization of (E)-6-(3,4-dimethoxyphenyl)-1-ethyl-4-mesitylimino-3-methyl- 3,4-dihydro-2(1H)-pyrimidinone polymorphs.

PubMed

Miyamae, A; Kitamura, S; Tada, T; Koda, S; Yasuda, T

1991-10-01

The polymorphism of (E)-6-(3,4-dimethoxyphenyl)-1-ethyl-4-mesitylimino-3-methyl-3,4-di hydro- 2(1 H)-pyrimidinone (FK664; 1) was characterized by using X-ray powder diffractometry, differential scanning calorimetry (DSC), and IR spectroscopy. Structures of two polymorphs (Forms A and B) were determined by X-ray crystallographic analysis. Form A crystallized in the monoclinic space group P2(1)/c, with a = 13.504(2), b = 6.733(1), c = 24.910(8) A, beta = 96.55(4) degrees, z = 4, and dcal = 1.203 g/cm3, while Form B crystallized in the same space group, with a = 8.067(2), b = 15.128(4), c = 18.657(4) A, beta = 102.34(3) degrees, z = 4, and dcal = 1.216 g/cm3. The conformational features of 1 were very similar between the two polymorphs. Compound 1, in both crystal forms, took an energetically reasonable conformation in three rigid planes, such as 2-pyrimidone, trimethylphenyl, and dimethoxyphenyl rings, but the molecules were packed in different ways between the two polymorphs. In the Form B crystal, a short contact was possible, to form pi-pi interactions between two dimethoxyphenyl groups related with the inversion center in the crystal lattice; this interaction seems to contribute to stabilizing the crystal structure of Form B. Both Forms A and B showed only one endothermic peak due to fusion at 115 and 140 degrees C, respectively, on the DSC thermograms; therefore, it is suggested that there are no transition points between the two polymorphs. The heats of fusion obtained from the DSC thermograms were 33.2(2) kJ/mol for Form A and 36.8(1) kJ/mol for Form B.(ABSTRACT TRUNCATED AT 250 WORDS)

A new anion-deficient fluorite-related superstructure of Bi{sub 28}V{sub 8}O{sub 62}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Đorđević, T., E-mail: tamara.djordjevic@univie.ac.at; Karanović, Lj., E-mail: ljika2002@yahoo.com

2014-12-15

New hydrothermally synthesized Bi{sub 28}V{sub 8}O{sub 62} was structurally characterized using single-crystal X-ray diffraction data. Bi{sub 28}V{sub 8}O{sub 62} crystallizes in the novel type of defect fluorite structure related to the face-centered cubic δ-Bi{sub 2}O{sub 3}. It is monoclinic, s. g. P2{sub 1}/c, and the relation to the fluorite subcell is given as a∼(3/2)a{sub F}+(3/2)c{sub F}; b∼ −b{sub F}; c∼2a{sub F} −4c{sub F} (F in subscript indicate the unit cell parameter of fluorite). Its structure is characterized by slabs of edge sharing OBi{sub 4} tetrahedra surrounded by the OBi{sub 3} triangles. As a part of these OBi{sub 3} triangles, twomore » positionally disordered Bi{sup 3+} cations were observed in the marginal part of the slabs. The slabs are extending along b axis and are linked by inter-slab portion of the structure composed of VO{sub 4} tetrahedra and BiO{sub 6−x} coordination polyhedra, where x is a number of vacant oxygen sites. Raman spectra verified the coordination environment of vanadium atoms in the structure. - Graphical abstract: The [4{sup ¯}01] projection of two slabs and inter-slab part of the structure in one layer parallel to the (3{sup ¯}08)=(002{sup ¯}){sub F} plane (F in subscript indicate a fluorite type structure). The large green circles are Bi atoms. Small blue circles represent partly and fully occupied O sites, respectively. Pink (hatched black) are V1O{sub 4} and blue (hatched white) are V2O{sub 4} coordination tetrahedra. - Highlights: • Single crystals of Bi{sub 28}V{sub 8}O{sub 62} were grown using hydrothermal technique. • The crystal structure of Bi{sub 28}V{sub 8}O{sub 62} was solved using single-crystal XRD method. • Bi{sub 28}V{sub 8}O{sub 62} has an anion-deficient fluorite-related superstructure. • Raman spectrum confirmed the coordination environment of vanadium atoms. • Relation to the structurally related compound was discussed.« less

Engineering Solid-State Materials. Strategies for Modeling and Packing Control of Molecular Assemblies into 3-D Networks

DTIC Science & Technology

1993-04-22

cocrystal /materials design/hydrogen bonding 19 ABSTRACT (Continue on reverse if necessary and identify by block number) The crystal structure and...proterties of a number of urea cocrystals are studied with regard to symmetry of the hydrogen-bonded molecular assemblies. The logical consequences of...symmetry element A or M. ¶/or 2 Results: Our specific goals are to design and synthesize urea based cocrystals in which the twofold symmetry and hydrogen

X-ray crystal structure of the passenger domain of plasmid encoded toxin(Pet), an autotransporter enterotoxin from enteroaggregative Escherichia coli (EAEC)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Domingo Meza-Aguilar, J.; Laboratorio de Patogenicidad Bacteriana, Unidad de Hemato Oncología e Investigación, Hospital Infantil de México Federico Gómez 06720, D.F.; Fromme, Petra

Highlights: • X-ray crystal structure of the passenger domain of Plasmid encoded toxin at 2.3 Å. • Structural differences between Pet passenger domain and EspP protein are described. • High flexibility of the C-terminal beta helix is structurally assigned. - Abstract: Autotransporters (ATs) represent a superfamily of proteins produced by a variety of pathogenic bacteria, which include the pathogenic groups of Escherichia coli (E. coli) associated with gastrointestinal and urinary tract infections. We present the first X-ray structure of the passenger domain from the Plasmid-encoded toxin (Pet) a 100 kDa protein at 2.3 Å resolution which is a cause ofmore » acute diarrhea in both developing and industrialized countries. Pet is a cytoskeleton-altering toxin that induces loss of actin stress fibers. While Pet (pdb code: 4OM9) shows only a sequence identity of 50% compared to the closest related protein sequence, extracellular serine protease plasmid (EspP) the structural features of both proteins are conserved. A closer structural look reveals that Pet contains a β-pleaded sheet at the sequence region of residues 181–190, the corresponding structural domain in EspP consists of a coiled loop. Secondary, the Pet passenger domain features a more pronounced beta sheet between residues 135 and 143 compared to the structure of EspP.« less

Metal–organic coordination architectures of tetrazole heterocycle ligands bearing acetate groups: Synthesis, characterization and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Bo-Wen, E-mail: bowenhu@hit.edu.cn; Zheng, Xiang-Yu; Ding, Cheng

2015-12-15

Two new coordination complexes with tetrazole heterocycle ligands bearing acetate groups, [Co(L){sub 2}]{sub n} (1) and [Co{sub 3}(L){sub 4}(N{sub 3}){sub 2}·2MeOH]{sub n} (2) (L=tetrazole-1-acetate) have been synthesized and structurally characterized. Single crystal structure analysis shows that the cobalt-complex 1 has the 3D 3,6-connected (4{sup 2}.6){sub 2}(4{sup 4}.6{sup 2}.8{sup 8}.10)-ant topology. By introducing azide in this system, complex 2 forms the 2D network containing the [Co{sub 3}] units. And the magnetic properties of 1 and 2 have been studied. - Graphical abstract: The synthesis, crystal structure, and magnetic properties of the new coordination complexes with tetrazole heterocycle ligands bearing acetate groupsmore » are reported. - Highlights: • Two novel Cobalt(II) complexes with tetrazole acetate ligands were synthesized. • The magnetic properties of two complexes were studied. • Azide as co-ligand resulted in different structures and magnetic properties. • The new coordination mode of tetrazole acetate ligand was obtained.« less

Synthesis, crystal structure and catalytic effect on thermal decomposition of RDX and AP: An energetic coordination polymer [Pb{sub 2}(C{sub 5}H{sub 3}N{sub 5}O{sub 5}){sub 2}(NMP)·NMP]{sub n}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jin-jian; Yancheng Teachers College, Yancheng 224002; Liu, Zu-Liang, E-mail: liuzl@mail.njust.edu.cn

2013-04-15

An energetic lead(II) coordination polymer based on the ligand ANPyO has been synthesized and its crystal structure has been got. The polymer was characterized by FT-IR spectroscopy, elemental analysis, DSC and TG-DTG technologies. Thermal analysis shows that there are one endothermic process and two exothermic decomposition stages in the temperature range of 50–600 °C with final residues 57.09%. The non-isothermal kinetic has also been studied on the main exothermic decomposition using the Kissinger's and Ozawa–Doyle's methods, the apparent activation energy is calculated as 195.2 KJ/mol. Furthermore, DSC measurements show that the polymer has significant catalytic effect on the thermal decompositionmore » of ammonium perchlorate. - Graphical abstract: An energetic lead(II) coordination polymer of ANPyO has been synthesized, structurally characterized and properties tested. Highlights: ► We have synthesized and characterized an energetic lead(II) coordination polymer. ► We have measured its molecular structure and thermal decomposition. ► It has significant catalytic effect on thermal decomposition of AP.« less

Increasing the electron-transfer ability of Cyanidioschyzon merolae ferredoxin by a one-point mutation – A high resolution and Fe-SAD phasing crystal structure analysis of the Asp58Asn mutant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ueno, Yuko; Matsumoto, Takashi; Yamano, Akihito

2013-07-12

Highlights: •A single amino acid change on the ferredoxin surface affects electron transfer. •Precise positions of amide atoms were located utilizing no prior structural data. •Ultra high resolution and SAD phasing may be used for bias-free model building. -- Abstract: Cyanidioschyzon merolae (Cm) is a single cell red algae that grows in rather thermophilic (40–50 °C) and acidic (pH 1–3) conditions. Ferredoxin (Fd) was purified from this algae and characterized as a plant-type [2Fe–2S] Fd by physicochemical techniques. A high resolution (0.97 Å) three-dimensional structure of the CmFd D58N mutant molecule has been determined using the Fe-SAD phasing method tomore » clarify the precise position of the Asn58 amide, as this substitution increases the electron-transfer ability relative to wild-type CmFd by a factor of 1.5. The crystal structure reveals an electro-positive surface surrounding Asn58 that may interact with ferredoxin NADP{sup +} reductase or cytochrome c.« less

Measurements of Shock Effects Recorded by Hayabusa Samples

NASA Technical Reports Server (NTRS)

Zolensky, Michael; Mikouchi, Takashi; Hagiya, Kenji; Ohsumi, Kazumasa; Martinez, James; Komatsu, Mutsumi; Chan, Queenie H-.S.

2015-01-01

We requested and have been approved for 5 Hayabusa samples in order definitively establish the degree of shock experienced by the regolith of asteroid Itokawa, and to devise a bridge between shock determinations by standard light optical petrography, crystal structures as determined by synchrotron X-ray diffraction (SXRD), and degree of crystallinity as determined by electron back-scattered diffraction (EBSD) [1,2]. As of the writing of this abstract we are awaiting the approved samples. We propose measurements of astromaterial crystal structures and regolith processes. The proposed research work will improve our understanding of how small, primitive solar system bodies formed and evolved, and improve understanding of the processes that determine the history and future of habitability of environments on other solar system bodies. The results of the proposed research will directly enrich the ongoing asteroid and comet exploration missions by NASA, JAXA and ESA, and broaden our understanding of the origin and evolution of small bodies in the early solar system, and elucidate the nature of asteroid and comet regolith.

Measurements of Shock Effects Recorded by Itokawa Samples

NASA Technical Reports Server (NTRS)

Zolensky, Michael; Mikouchi, Takashi; Hagiya, Kenji; Ohsumi, Kazumasa; Martinez, James; Komatsu, Mutsumi; Chan, Queenie H-.S.

2016-01-01

We requested and have been approved for 5 Hayabusa samples in order definitively establish the degree of shock experienced by the regolith of asteroid Itokawa, and to devise a bridge between shock determinations by standard light optical petrography, crystal structures as determined by synchrotron X-ray diffraction (SXRD), and degree of crystallinity as determined by electron back-scattered diffraction (EBSD). As of the writing of this abstract we are awaiting the approved samples. We propose measurements of astromaterial crystal structures and regolith processes. The proposed research work will improve our understanding of how small, primitive solar system bodies formed and evolved, and improve understanding of the processes that determine the history and future of habitability of environments on other solar system bodies. The results of the proposed research will directly enrich the ongoing asteroid and comet exploration missions by NASA, JAXA and ESA, and broaden our understanding of the origin and evolution of small bodies in the early solar system, and elucidate the nature of asteroid and comet regolith.

LDEF: A bibliography with abstracts

NASA Technical Reports Server (NTRS)

Gouger, H. Garland (Editor)

1992-01-01

The Long Duration Exposure Facility (LDEF) was a free-flying cylindrical structure that housed self-contained experiments in trays mounted on the exterior of the structure. Launched into orbit from the Space Shuttle Challenger in 1984, the LDEF spent almost six years in space before being recovered in 1990. The 57 experiments investigated the effects of the low earth orbit environment on materials, coatings, electronics, thermal systems, seeds, and optics. It also carried experiments that measured crystals growth, cosmic radiation, and micrometeoroids. This bibliography contains 435 selected records from the NASA aerospace database covering the years 1973 through June of 1992. The citations are arranged within subject categories by author and date of publication.

Precursor routes to quaternary intermetallics: Synthesis, crystal structure, and physical properties of clathrate-II Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Kaya; Dong, Yongkwan; Nolas, George S., E-mail: gnolas@usf.edu

A new quaternary clathrate–II composition, Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112}, was synthesized by kinetically controlled thermal decomposition (KCTD) employing both NaSi and NaAlSi as the precursors and CsCl as a reactive flux. The crystal structure and composition of Cs{sub 8}Na{sub 16}Al{sub 24}Si{sub 112} were investigated using both Rietveld refinement and elemental analysis, and the temperature dependent transport properties were investigated. Our results indicate that KCTD with multiple precursors is an effective method for the synthesis of multinary inorganic phases that are not easily accessible by traditional solid-state synthesis or crystal growth techniques. - Graphical abstract: Quaternary Cs{sub 8}Na{sub 16}Al{sub 24}S{submore » 112} clathrate–II was synthesized for the first time by kinetically controlled thermal decomposition (KCTD) employing a NaSi+NaAlSi precursor mixture with CsCl as the reactive flux, and the structural and transport properties were investigated. Our approach demonstrates a new synthetic pathway for the synthesis of multinary inorganic compounds. This work reports the exploration of a new clathrate composition as this class of materials continues to be of interest for thermoelectrics and other energy-related applications.« less

Metal Insulator transition in Vanadium Dioxide

NASA Astrophysics Data System (ADS)

Jovaini, Azita; Fujita, Shigeji; Suzuki, Akira; Godoy, Salvador

2012-02-01

MAR12-2011-000262 Abstract Submitted for the MAR12 Meeting of The American Physical Society Sorting Category: 03.9 (T) On the metal-insulator-transition in vanadium dioxide AZITA JOVAINI, SHIGEJI FUJITA, University at Buffalo, SALVADOR GODOY, UNAM, AKIRA SUZUKI, Tokyo University of Science --- Vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340 K with the structural change from tetragonal to monoclinic crystal. The conductivity _/ drops at MIT by four orders of magnitude. The low temperature monoclinic phase is known to have a lower ground-state energy. The existence of the k-vector k is prerequisite for the conduction since the k appears in the semiclassical equation of motion for the conduction electron (wave packet). The tetragonal (VO2)3 unit is periodic along the crystal's x-, y-, and z-axes, and hence there is a three-dimensional k-vector. There is a one-dimensional k for a monoclinic crystal. We believe this difference in the dimensionality of the k-vector is the cause of the conductivity drop. Prefer Oral Session X Prefer .

Promoting crystallisation of the Salmonella enteritidis fimbriae 14 pilin SefD using deuterium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Bing; Garnett, James A.; Lee, Wei-chao

Highlights: Black-Right-Pointing-Pointer The benefits of D{sub 2}O in screening for crystallisation was explored. Black-Right-Pointing-Pointer The crystal structures of the SefD pilin in both H{sub 2}O and D{sub 2}O reveal differences. Black-Right-Pointing-Pointer Crystallisation improvements are explained by altered interactions in D{sub 2}O crystals. Black-Right-Pointing-Pointer D{sub 2}O is useful additive in sparse-matrix screening for crystallisation. -- Abstract: The use of heavy water (D{sub 2}O) as a solvent is commonplace in many spectroscopic techniques for the study of biological macromolecules. A significant deuterium isotope effect exists where hydrogen-bonding is important, such as in protein stability, dynamics and assembly. Here we illustrate the usemore » of D{sub 2}O in additive screening for the production of reproducible diffraction-quality crystals for the Salmonella enteritidis fimbriae 14 (SEF14) putative tip adhesin, SefD.« less

Potassium and magnesium succinatouranilates – Synthesis and crystal structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Novikov, S.A., E-mail: serg.alex.novikov@gmail.com; Grigoriev, M.S.; Serezhkina, L.B.

2017-04-15

Single crystal X-ray diffraction has been applied to determine the structures of two new uranyl coordination polymers: K{sub 2}[(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}] (1) and [Mg(H{sub 2}O){sub 6}] [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]·2H{sub 2}O (2), where C{sub 4}H{sub 4}O{sub 4}{sup 2-} is succinate anion. Crystals of 1 and 2 contain polymeric complex anions [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]{sup 2-} with the same A{sub 2}Q{sup 02}{sub 3} crystallochemical formula (A=UO{sub 2}{sup 2+}, Q{sup 02}=C{sub 4}O{sub 4}H{sub 4}{sup 2-}), and have layered (1) or chain (2) structure. It has been found, that conformation of succinate ionsmore » is one of the factors, which affects the structure of [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]{sup 2-} anions. IR spectra of these new compounds are in good agreement with crystallographic data. Topological analysis of the uranium dicarboxylates with A{sub 2}Q{sup 02}{sub 3} crystallochemical formula has shown the presence of five isomers which differ from each other in coordination sequences and / or dimensionality. - Graphical abstract: Crystal structures of two new uranium(VI) coordination polymers with succinate linkers, namely K{sub 2}[(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}] (1) and [Mg(H{sub 2}O){sub 6}][(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]·2H{sub 2}O (2), were determined by single-crystal XRD. Crystals of studied compounds are based on 2D or 1D structural units with the same composition and crystallochemical formula. Topological isomerism in A{sub 2}Q{sup 02}{sub 3} crystallochemical group and conformations of succinate anions in uranyl complexes are under discussion. - Highlights: • Two new uranium coordination polymers were synthesized. • Their structural units have the same composition and crystallochemical formula. • In spite the same composition and CCF dimensionality of units is different. • Structural features of uranyl CPs are affected by linker conformations.« less

Dehydration-driven evolution of topological complexity in ethylamonium uranyl selenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Krivovichev, Sergey V.; Tananaev, Ivan G.

Single crystals of four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules, (C{sub 2}H{sub 8}N){sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) (I), (C{sub 2}H{sub 8}N){sub 3}[(UO{sub 2})(SeO{sub 4}){sub 2}(HSeO{sub 4})] (II), (C{sub 2}H{sub 8}N)[(UO{sub 2})(SeO{sub 4})(HSeO{sub 3})] (III), and (C{sub 2}H{sub 8}N)(H{sub 3}O)[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (IV) have been prepared by isothermal evaporation from aqueous solutions. Uranyl-containing 1D and 2D units have been investigated using topological approach and information-based complexity measurements that demonstrate the evolution of structural units and the increase of topological complexity with the decrease of H{sub 2}O content. - Graphical abstract: Single crystals ofmore » four novel uranyl selenate and selenite-selenate oxysalts with protonated ethylamine molecules have been prepared by isothermal evaporation from aqueous solutions. Structural analysis and information-based topological complexity calculations points to the possible sequence of crystalline phases formation, showing both topological and structural branches of evolution. - Highlights: • Single crystals of four novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • Dehydration processes drives the evolution of topological complexity of 1D and 2D structural units.« less

Synthesis, crystal structure and optical properties of two new layered cadmium iodates: Cd(IO{sub 3})X (X=Cl, OH)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Bing-Ping, E-mail: ybp@fjirsm.ac.cn; Mao, Jiang-Gao

Systematic explorations of new compounds in the cadmium iodate system by hydrothermal reactions led to two layered iodates, namely, Cd(IO{sub 3})X (X=Cl, OH). Cd(IO{sub 3})Cl crystallizes in the orthorhombic space group Cmca (No. 64) whereas Cd(IO{sub 3})(OH) crystallizes in the orthorhombic space group Pnma (No. 62). Cd(IO{sub 3})Cl displays a unique double layered structure composed of {sup 1}{sub ∞}[Cd−O{sub 3}Cl]{sub n} chains. Cadmium octahedrons form a 1D chain along the a-axis through edge sharing, and such chains are further interconnected via IO{sub 3} groups to form a special double layer on (020) plane. Cd(IO{sub 3})(OH) also exhibits a layered structuremore » that is composed of cadmium cations, IO{sub 3} groups and hydroxyl ions. Within a layer, chains of CdO{sub 6} edge-shared octahedra are observed along the b-axis. And these chains are connected by IO{sub 3} groups into a layer parallel to the bc plane. Spectroscopic characterizations, elemental analysis, and thermogravimetric analysis for the reported two compounds are also presented. - Graphical abstract: Two new layered cadmium iodates Cd(IO{sub 3})X (X=Cl, OH) are reported. Cd(IO{sub 3})Cl features a unique double layered structure whereas Cd(IO{sub 3})(OH) displays an ordinary layered structure. - Highlights: • Two new layered cadmium iodates Cd(IO{sub 3})X (X=Cl, OH) are reported. • Cd(IO{sub 3})Cl features a unique double layered structure. • Cd(IO{sub 3})(OH) displays an ordinary layered structure. • The spectroscopic and thermal properties have been studied in detail.« less

Structural insights into the thermal decomposition sequence of barium tetrahydrogenorthotellurate(VI), Ba[H{sub 4}TeO{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weil, Matthias, E-mail: Matthias.Weil@tuwien.ac.at; Stöger, Berthold; Gierl-Mayer, Christian

2016-09-15

The compounds Ba[H{sub 4}TeO{sub 6}] (I), Ba[H{sub 2}TeO{sub 5}] (II), Ba[Te{sub 2}O{sub 6}(OH){sub 2}] (III) and Ba[TeO{sub 4}] (IV) were prepared by application of a diffusion method (I), under hydrothermal conditions (II and III) and from solid state reactions (IV), respectively. Structure analysis on the basis of single crystal X-ray diffraction data revealed novel structure types for (I), (II) and (III) and isotypism of (IV) with PrSbO{sub 4} and LaSbO{sub 4}. Common feature of the four oxotellurate(VI) structures are [TeO{sub 6}] octahedra. Whereas in the crystal structure of (I) the octahedral units are isolated, they are condensed into chains viamore » corner-sharing in (II) and via edge-sharing in (III) and (IV). The coordination numbers of the barium cations in the four structures range from seven to ten. Although hydrogen atom positions could not be located for the structures of (I) and (II), short interpolyhedral O···O contacts are evident for strong hydrogen bonding. The temperature behaviour of (I), (II) and (IV) was monitored by simultaneous thermal analysis (STA) measurements and in situ powder X-ray diffraction, revealing the decomposition sequence Ba[H{sub 4}TeO{sub 6}] → Ba[H{sub 2}TeO{sub 5}] → Ba[TeO{sub 4}]→ Ba[TeO{sub 3}] upon heating to temperatures up to 900 °C. - Graphical abstract: The crystal structures of the four oxotellurates(VI) were determined from single crystal data. The thermal decomposition of Ba[H{sub 4}TeO{sub 6}], monitored by temperature-dependent X-ray powder diffraction and simultaneous thermal analysis measurements, involves two condensation reactions according to Ba[H{sub 4}TeO{sub 6}]→Ba[H{sub 2}TeO{sub 5}]+H{sub 2}O(↑)→Ba[TeO{sub 4}]+ H{sub 2}O(↑). Display Omitted.« less

Transmission electron microscopy study of the MgS–Tm{sub 2}S{sub 3} system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Varadé-López, R., E-mail: rebeca.varade@ucm.es; Ávila-Brande, D., E-mail: davilabr@ucm.es; Urones-Garrote, E., E-mail: esteban.urones@pdi.ucm.es

2015-09-15

This work presents the structural–microstructural characterization of the NaCl-derivative MgS–Tm{sub 2}S{sub 3} system, which can be formulated by the expression Mg{sub (1−x)}Tm{sub (2/3)x}□{sub (1/3)x}S (□→cation vacancy). Transmission electron microscopy observations show the transition between NaCl-type and spinel-type structures when 0 ≤x≤ 0.75. The increase of Tm content in the solid solution provokes the increase of the spinel-type phase proportion, which intergrows with the NaCl-type crystals. When x≥0.75, some phases derived from NaCl-type structure through the chemical twinning at the unit cell level crystallographic operation are observed, such as CT-MgTm{sub 2}S{sub 4} and CT-MgTm{sub 4}S{sub 7}. The existence and nature ofmore » the extended defects observed along the c direction of these structures are characterized by means of Scanning-Transmission electron microscopy high-angle dark field imaging, which allows observing the presence of quasi ordered crystals with new possible complex stoichiometries at atomic resolution. - Graphical abstract: HAADF-STEM image of a disordered CT-MgYb{sub 2}S{sub 4} crystal. The disordered twin-slab sequences are marked by arrows. - Highlights: • Structural evolution of the Mg{sub (1−x)}Tm{sub (2/3)x}□{sub (1/3)x}S system was characterized by means of TEM. • The increase in Tm content provokes the transition from NaCl to spinel-type structure up to x=0.75. • Chemical twinned phases CT-MgTm{sub 2}S{sub 4} and CT-MgTm{sub 4}S{sub 7} are observed at high Tm contents. • Extended defects in CT-crystals are characterized with atomic resolution STEM-HAADF images.« less

Crystal growth methods dedicated to low solubility actinide oxalates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tamain, C., E-mail: christelle.tamain@cea.fr; Arab-Chapelet, B.; Rivenet, M.

Two novel crystal growth syntheses dedicated to low solubility actinide-oxalate systems and adapted to glove box handling are described. These methods based on the use of precursors of either actinide metal or oxalic acid have been optimized on lanthanide systems (analogue of actinides(III)) and then assessed on real actinide systems. They allow the synthesis of several actinide oxalate single crystals, Am{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 3}·xH{sub 2}O, Th(C{sub 2}O{sub 4}){sub 2}·6H{sub 2}O, M{sub 2+x}[Pu{sup IV}{sub 2−x}Pu{sup III}{sub x}(C{sub 2}O{sub 4}){sub 5}]·nH{sub 2}O and M{sub 1−x}[Pu{sup III}{sub 1−x}Pu{sup IV}{sub x}(C{sub 2}O{sub 4}){sub 2}·H{sub 2}O]·nH{sub 2}O. It is the first timemore » that these well-known compounds are formed by crystal growth methods, thus enabling direct structural studies on transuranic element systems and acquisition of basic data beyond deductions from isomorphic (or not) lanthanide compounds. Characterizations by X-ray diffraction, UV–visible solid spectroscopy, demonstrate the potentialities of these two crystal growth methods to obtain oxalate compounds. - Graphical abstract: Two new single crystal growth methods dedicated to actinide oxalate compounds. - Highlights: • Use of diester as oxalate precursor for crystal growth of actinide oxalates. • Use of actinide oxide as precursor for crystal growth of actinide oxalates. • Crystal growth of Pu(III) and Am(III) oxalates. • Crystal growth of mixed Pu(III)/Pu(IV) oxalates.« less

Synthesis and characterization of zinc borophosphates with ANA-zeotype framework by the microwave method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, Yu, E-mail: songyu@dlpu.edu.cn; Ding, Ling; An, Qingda

2013-06-15

Zinc borophosphate (NH{sub 4}){sub 16}[Zn{sub 16}B{sub 8}P{sub 24}O{sub 96}] (denoted as ZnBP-ANA) with ANA-zeotype structure has been synthesized by employing microwave-assisted solvothermal synthesis in the reaction system ZnCl{sub 2}∙6H{sub 2}O-(NH{sub 4}){sub 2}HPO{sub 4}–H{sub 3}BO{sub 3} using ethylene glycol as a co-solvent. The influences of various experimental parameters, such as reaction temperature, solvent ratio, zinc precursors and reactive power, have been systematically investigated. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA), and so on. Small and homogeneous ZnBP-ANA single crystal with regular cube morphology are crystallized by using microwave solvothermal synthesis method withinmore » a shorter time, and its grain size decreases with power. - Graphical abstract: Tailor-made ANA zeolites with varied size can be prepared by simply changing the reaction power. - Highlights: • Zinc borophosphate zeolites with ANA-zeotype structures were prepared by microwave technique. • The size of crystals could be controlled by tuning power. • Synthesis period can be significantly reduced by raising reaction temperature.« less

Synthesis, characterization and computational study of the newly synthetized sulfonamide molecule

NASA Astrophysics Data System (ADS)

Murthy, P. Krishna; Suneetha, V.; Armaković, Stevan; Armaković, Sanja J.; Suchetan, P. A.; Giri, L.; Rao, R. Sreenivasa

2018-02-01

A new compound N-(2,5-dimethyl-4-nitrophenyl)-4-methylbenzenesulfonamide (NDMPMBS) has been derived from 2,5-dimethyl-4-nitroaniline and 4-methylbenzene-1-sulfonyl chloride. Structure was characterized by SCXRD studies and spectroscopic tools. Compound crystallized in the monoclinic crystal system with P21/c space group a = 10.0549, b = 18.967, c = 8.3087, β = 103.18 and Z = 4. Type and nature of intermolecular interaction in crystal state investigated by 3D-Hirshfeld surface and 2D-finger print plots revealed that title compound stabilized by several interactions. The structural and electronic properties of title compound have been calculated at DFT/B3LYP/6-311G++(d,p) level of theory. Computationally obtained spectral data was compared with experimental results, showing excellent mutual agreement. Assignment of each vibrational wave number was done on the basis of potential energy distribution (PED). Investigation of local reactivity descriptors encompassed visualization of molecular electrostatic potential (MEP) and average local ionization energy (ALIE) surfaces, visualization of Fukui functions, natural bond order (NBO) analysis, bond dissociation energies for hydrogen abstraction (H-BDE) and radial distribution functions (RDF) after molecular dynamics (MD) simulations. MD simulations were also used in order to investigate interaction of NDMPMBS molecule with 1WKR and 3ETT proteins protein.

Bi-substituted iron garnet films for one-dimensional magneto-photonic crystals: Synthesis and properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaposhnikov, A.N.; Karavainikov, A.V.; Prokopov, A.R.

2012-06-15

Graphical abstract: Faraday hysteresis loops for Bi{sub 1.0}Y{sub 0.5}Gd{sub 1.5}Fe{sub 4.2}Al{sub 0.8}O{sub 12} film on glass-ceramic substrate (a), Bi{sub 2.8}Y{sub 0.2}Fe{sub 5}O{sub 12} film on gallium–gadolinium garnet (b) and for glass-ceramic/SiO{sub 2}/Bi{sub 1.0}Y{sub 0.5}Gd{sub 1.5}Fe{sub 4.2}Al{sub 0.8}O{sub 12}/Bi{sub 2.8}Y{sub 0.2}Fe{sub 5}O{sub 12} structure (c). Highlights: ► Bismuth-substituted iron garnet films as magneto-optical layers in magneto-photonic crystals. ► It is impossible to crystallize the films with high Bi content on amorphous substrates. ► The crystallization of the films can be achieved by their deposition on buffer layer with low bismuth content. -- Abstract: The crystallization processes in Bi{sub 2.8}Y{sub 0.2}Fe{sub 5}O{submore » 12}, Bi{sub 2.5}Gd{sub 0.5}Fe{sub 3.8}Al{sub 1.2}O{sub 12}, Bi{sub 1.5}Gd{sub 1.5}Fe{sub 4.5}Al{sub 0.5}O{sub 12} and Bi{sub 1.0}Y{sub 0.5}Gd{sub 1.5}Fe{sub 4.2}Al{sub 0.8}O{sub 12} garnet films deposited by reactive ion beam sputtering on (1 1 1) gadolinium–gallium garnet substrates, optical glass-ceramic and SiO{sub 2} films have been studied. Films were annealed at low pressure in oxygen atmosphere and in the air. The possibility of preparation of crystalline garnet films with high concentration of bismuth on the SiO{sub 2} films using a buffer layer with low concentration of Bi has been shown. This allows to produce one-dimensional magneto-photonic crystals with high effective Faraday rotation (several tens of°/μm for the visible optical spectrum).« less

Structure refinement for tantalum nitrides nanocrystals with various morphologies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Lianyun; School of Science, Beijing Jiaotong University, 3 Shang Yuan Cun, Haidian District, Beijing 100044; Huang, Kai

2012-07-15

Graphical abstract: Tantalum nitrides nanocrystals with various phases and morphologies for the first time have been synthesized through homogenous sodium reduction under low temperature with the subsequent annealing process under high vacuum. Highlights: ► The spherical TaN, cuboidal TaN{sub 0.83} and TaN{sub 0.5} nanocrystals have been synthesized through homogenous sodium reduction under low temperature with the subsequent annealing process under high vacuum. ► The crystal structures of different tantalum nitrides were determined by Rietveld refinement on the X-ray diffraction data and the examinations of electron microcopies. ► The specific surface area of the tantalum nitrides powders was around 10 m{supmore » 2} g{sup −1}. ► Tantalum nitrides powders could be suitable for capacitor with high specific capacitance. -- Abstract: Tantalum nitrides (TaN{sub x}) nanocrystals with different phase and morphology have been synthesized through homogenous sodium reduction under low temperature with the subsequent annealing process under high vacuum. The crystal structures of tantalum nitrides were determined by Rietveld refinement based on the X-ray diffraction data. The morphologies of various tantalum nitrides nanocrystals in high quality were analyzed through the electron microcopies examinations. The spherical TaN nanoparticles, cuboidal TaN{sub 0.83} and TaN{sub 0.5} nanocrystals have been selectively prepared at different annealing temperatures. In addition, the specific surface areas of the tantalum nitrides nanocrystals measured by BET method were around 9.87–11.64 m{sup 2} g{sup −1}, indicating that such nano-sized tantalum nitrides could be suitable for capacitor with high specific capacitance.« less

The cluster compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} containing Mo{sub 14} clusters and the new mono- and bi-capped trioctahedral Mo{sub 15} and Mo{sub 16} clusters: Synthesis, crystal structure, and electrical and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gall, Philippe; Guizouarn, Thierry; Gougeon, Patrick, E-mail: Patrick.Gougeon@univ-rennes1.fr

2015-07-15

Single crystals of the new quaternary compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} were obtained by solid state reaction. The crystal structure was determined by single-crystal X-ray diffraction. In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} crystallizes in the orthorhombic space group Pbca with unit-cell parameters a=9.4432(14) Å, b=11.4828(12) Å, c=20.299(4) Å and Z=4. Full-matrix least-squares refinement on F{sup 2} using 3807 independent reflections for 219 refinable parameters resulted in R{sub 1}=0.0259 and wR{sub 2}=0.0591. The crystal structure contains in addition to Mo{sub 14} clusters the first examples of mono- and bi-capped trioctahedral Mo{sub 14} i.e. Mo{sub 15} and Mo{sub 16} clusters.more » The oxygen framework derives from a stacking along the a direction of close-packed layers with sequence (…ABAC…). The Mo–Mo distances range between 2.6938(5) and 2.8420(6) Å and the Mo–O distances between 1.879(5) and 2.250(3) Å, as usually observed in molybdenum oxide clusters. The indium atoms form In{sub 4}{sup 6+} bent chains with In–In distances of 2.6682(5) and 2.6622(8) Å and the Ti atoms are in highly distorted octahedral sites of oxygen atoms with Ti–O distances ranging between 1.865(4) and 2.161(4) Å. Magnetic susceptibility measurements confirm the presence of Ti{sup 4+} cations and the absence of localized moments on the Mo network. Electrical resistivity measurements on a single crystal of In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} show a semimetallic behavior. - Graphical abstract: We present here the synthesis, the crystal structure, and the electrical and magnetic properties of the new compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} in which Mo{sub 14} clusters coexist statistically with mono- and bi-capped trioctahedral Mo{sub 14} that is Mo{sub 15} and Mo{sub 16} clusters. - Highlights: • Single crystals of In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} were obtained by solid state reaction. • The crystal structure contains Mo{sub 14}, Mo{sub 15} and Mo{sub 16} clusters. • The indium atoms form In{sub 4}{sup 6+} bent chains. • Poorly metallic behavior. • Absence of localized moments on the Mo network as well as on the Ti atoms.« less

Dynamic Photonic Materials Based on Liquid Crystals (Postprint)

DTIC Science & Technology

2013-09-01

AFRL-RX-WP-JA-2015-0059 DYNAMIC PHOTONIC MATERIALS BASED ON LIQUID CRYSTALS (POSTPRINT) Luciano De Sio and Cesare Umeton University...ON LIQUID CRYSTALS (POSTPRINT) 5a. CONTRACT NUMBER In-House 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) (see back...10.1016/B978-0-444-62644-8.00001-7. 14. ABSTRACT Liquid crystals, combining optical non-linearity and self-organizing properties with fluidity, and being

MULTICOMPONENT AEROSOL CRYSTALLIZATION. (R823980)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Surface defect free growth of a spin dimer TlCuCl{sub 3} compound crystals and investigations on its optical and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, Gihun, E-mail: G.Ryu@fkf.mpg.de; Son, Kwanghyo

A defect-free high quality single crystal of spin dimer TlCuCl{sub 3} compound is firstly synthesized at the optimal growth temperature using the vertical Bridgman method. In this study, we clearly found that the cupric chloride is easily decomposed into the Cl{sup −} deficient composition at ≥470 °C. The Cl{sup −}- related gas phase at the high temperature region also always gives rise to a pinhole-like surface defect at the surface of crystal. Therefore, we clearly verified an exotic anisotropic magnetic behavior (anisotropic ratio of M{sub b}/M{sub (201)} at 2 K, 7 T=10) using the defect-free TlCuCl{sub 3} crystals in thismore » three-dimensional spin dimer TlCuCl{sub 3} compound, relatively stronger magnetic ordering in the H//b than that of H//(201) direction at above the transition magnetic field. - Graphical abstract: A single crystal of spin dimer TlCuCl{sub 3} compound with a defect free is successfully synthesized on the basis of TG/DTA result. We newly found that this cupric chloride compound is easily decomposed into the Cl{sup −} deficient composition at ≥470 °C and Cl{sup −} related gas phases also give rise to the defects like a pinhole on the surface of TlCuCl{sub 3} crystal. Using the crystals with a surface defect free, we also clearly verified the crystal structure of spin dimer TlCuCl{sub 3} compound.« less

Crystal structures of the new ternary stannides La{sub 3}Mg{sub 4−x}Sn{sub 2+x} and LaMg{sub 3−x}Sn{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Solokha, P., E-mail: pavlo.solokha@unige.it; De Negri, S.; Minetti, R.

2016-01-15

Synthesis and structural characterization of the two new lanthanum–magnesium–stannides La{sub 3}Mg{sub 4−x}Sn{sub 2+x} (0.12≤x≤0.40) and LaMg{sub 3−x}Sn{sub 2} (0.33≤x≤0.78) are reported. The crystal structures of these intermetallics were determined by single crystal X-ray diffraction analysis and confirmed by Rietveld refinement of powder X-ray diffraction patterns of the corresponding samples. The La{sub 3}Mg{sub 4−x}Sn{sub 2+x} phase crystallizes in the hexagonal Zr{sub 3}Cu{sub 4}Si{sub 2} structure type (P6¯2m, hP9, Z=3, x=0.12(1), a=7.7974(7), c=4.8384(4) Å), which represents an ordered derivative of the hP9-ZrNiAl prototype, ubiquitous among equiatomic intermetallics. The LaMg{sub 3–x}Sn{sub 2} phase is the second representative of the trigonal LaMg{sub 3−x}Ge{sub 2}more » type, which is a superstructure of the LaLi{sub 3}Sb{sub 2} structure type (P3¯1c, hP34-0.12, Z=6, x=0.35(1), a=8.3222(9), c=14.9546(16) Å). The scheme describing the symmetry reduction/coloring with respect to the parent type is reported here with the purpose to discuss the LaMg{sub 3−x}Sn{sub 2} off-stoichiometry from the geometrical point of view. Structural relationships between the La–Mg–Sn ternary phases, including the already known equiatomic LaMgSn compound (oP12-TiNiSi), are presented in the framework of the AlB{sub 2}-related compounds family and discussed with the aid of group-subgroup relations in the Bärnighausen formalism. - Graphical abstract: Crystal structure of LaMg{sub 3−x}Sn{sub 2} viewed along the (001) direction together with the puckered layer of Mg and Sn atoms hosting Mg2, Mg3 and vacancy □. - Highlights: • Crystal structures of the new La{sub 3}Mg{sub 4−x}Sn{sub 2+x} and LaMg{sub 3−x}Sn{sub 2} phases were determined. • The off-stoichiometry of LaMg{sub 3−x}Sn{sub 2} was discussed from geometrical point of view. • Structural relations between the known La–Mg–Sn phases were established. • The studied compounds are related to the AlB{sub 2} type by symmetry reduction.« less

Tl{sub 10}Hg{sub 3}Cl{sub 16}: Single crystal growth, electronic structure and piezoelectric properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khyzhun, O.Y., E-mail: khyzhun@ipms.kiev.ua; Piasecki, M.; Kityk, I.V.

Single crystal of the ternary halide Tl{sub 10}Hg{sub 3}Cl{sub 16} was grown using Bridgman-Stockbarger method. For the Tl{sub 10}Hg{sub 3}Cl{sub 16} crystal, we have measured X-ray photoelectron spectra for both pristine and Ar{sup +} ion-bombarded surfaces and additionally investigated photoinduced piezoelectricity. Our data indicate that the Tl{sub 10}Hg{sub 3}Cl{sub 16} single crystal surface is very sensitive with respect to Ar{sup +} ion-bombardment. In particular, Ar{sup +} ion-bombardment with energy of 3.0 keV over 5 min at an ion current density of 14 μA/cm{sup 2} causes significant changes of the elemental stoichiometry of the Tl{sub 10}Hg{sub 3}Cl{sub 16} surface resulting inmore » an abrupt decrease of the mercury content in the top surface layers of the studied single crystal. As a result of the treatment, the mercury content becomes nil in the top surface layers. In addition, the present XPS measurements allow for concluding about very low hygroscopicity of the Tl{sub 10}Hg{sub 3}Cl{sub 16} single crystal surface. The property is extremely important for the crystal handling in optoelectronic or nano-electronic devices working at ambient conditions. The photoinduced piezoelectricity has been explored for Tl{sub 10}Hg{sub 3}Cl{sub 16} depending on nitrogen (λ=371 nm) laser power density and temperature. - Graphical abstract: As-grown single crystal boule of Tl{sub 10}Hg{sub 3}Cl{sub 16}; dependence of the effective piezoelecric coefficient d{sub 33} versus the photoinducing nitrogen laser power density, I, at different temperatures, T; and packing of the polyhedra of halide atoms around Hg atoms in the Tl{sub 10}Hg{sub 3}Cl{sub 16} structure. - Highlights: • High-quality Tl{sub 10}Hg{sub 3}Cl{sub 16} single crystal has been grown by Bridgman-Stockbarger method. • Electronic structure of Tl{sub 10}Hg{sub 3}Cl{sub 16} is studied by the XPS method. • Tl{sub 10}Hg{sub 3}Cl{sub 16} single crystal surface is sensitive with respect to Ar{sup +} ion-bombardment. • Very low hygroscopicity is characteristic of the Tl{sub 10}Hg{sub 3}Cl{sub 16} surface. • Photoinduced piezoelectricity is studied for the Tl{sub 10}Hg{sub 3}Cl{sub 16} compound.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osiry, H.; Cano, A.; Reguera, L.

The pentacyanonitrosylferrate complex anion, [Fe(CN){sub 5}NO]{sup 2−}, forms an insoluble solid with Hg(I) ion, of formula unit Hg{sub 2}[Fe(CN){sub 5}NO]·2H{sub 2}O, whose crystal structure and related properties are unknown. This contribution reports the preparation of that compound by the precipitation method and its structural study from X-ray powder patterns complemented with spectroscopic information from IR, Raman, and UV–vis techniques. The crystal structure was solved ab initio and then refined using the Rietveld method. The solid crystallizes with a triclinic unit cell, in the P−1 space group, with cell parameters a=10.1202(12), b=10.1000(13), c=7.4704(11) Å; α=110.664(10), β=110.114(10), γ=104.724(8) °. Within the unitmore » cell, two formula units are accommodated (Z=2). It adopts a layered structure related with the coordination of the equatorial CN groups at their N end to the Hg atoms while the axial CN ligand remains unlinked. Within the layers neighboring Hg{sub 2}[Fe(CN){sub 5}NO] building units remain linked through four relatively strong Hg–Hg interactions, with an interatomic distance of 2.549(3) Å. The charge donation from the equatorial CN groups through their 5σ orbitals results into an increase for the electron density on the Hg atoms, which strengths the Hg–Hg bond. In the Raman spectrum, that metal–metal bond is detected as a stretching vibration band at 167 cm{sup −1}. The available free volume between neighboring layers accommodates two water molecules, which are stabilized within the framework through hydrogen bonds with the N end of the unlinked axial CN group. The removal of these weakly bonded water molecules results in structural disorder for the material 3D framework. - Graphical abstract: Assembling of Hg{sub 2}[Fe(CN){sub 5}NO] units through Hg–Hg interactions. - Highlights: • Homometallic Hg–Hg interactions in metal nitroprusside. • 2D structure supported on metal–metal interactions. • Crystal structure and related properties for mercury (I) nitroprusside. • IR and UV–vis spectral features for mercury (I) nitroprusside.« less

Synthesis, crystal structure and magnetic properties of a new B-site ordered double perovskite Sr{sub 2}CuIrO{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasala, Sami; Yamauchi, Hisao; Karppinen, Maarit, E-mail: maarit.karppinen@aalto.fi

2014-12-15

Here we synthesize and characterize a new double-perovskite oxide Sr{sub 2}CuIrO{sub 6}. The synthesis requires the use of high oxygen pressure to stabilize the VI oxidation state of iridium. The compound has a tetragonally-distorted crystal structure due to the Jahn–Teller active Cu{sup II} ion, and a high degree of B-site cation order. Magnetic transition is apparent at 15 K, but the zero-field-cooled and field-cooled susceptibilities diverge below this temperature. The high degree of cation order would exclude the possibility of a typical spin-glass, indicating that the divergence is probably due to a frustration of the magnetic interactions between Cu andmore » Ir, with a high frustration factor of f≈25. - Graphical abstract: A new member of the A{sub 2}B′B″O{sub 6} double-perovskite family with JT-active Cu{sup II} at the B′ site and Ir{sup VI} at the B″ site is synthesized through high pressure synthesis and characterized for the structural and magnetic properties. - Highlights: • New member of the A{sub 2}CuB″O{sub 6} double-perovskite family is synthesized with B″=Ir. • Stabilization of Ir{sup VI} requires the use of high oxygen pressure synthesis. • Crystal structure is tetragonally distorted due to JT-active Cu{sup II}. • Divergence of ZFC and FC curves is seen below the T{sub N} of 15 K. • This is presumably due to a frustration effect.« less

On the symmetry and crystal structures of Ba{sub 2}LaIrO{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, W.T., E-mail: w.fu@chem.leidenuniv.n; Goetz, R.J.; IJdo, D.J.W.

2010-02-15

Accurate profile analysis of X-ray diffraction data was carried out to settle recent dispute on the symmetry and crystal structures of the double perovskite Ba{sub 2}LaIrO{sub 6}. Even through careful comparison of the full-width at half-maximum values, we found no evidence for Ba{sub 2}LaIrO{sub 6} adopting either monoclinic (I2/m) or mixed rhombohedral (R3-bar) and monoclinic (I2/m) structures at room temperature, becoming triclinic (I1-bar) at below about 200 K. The correct space group is just R3-bar at temperatures between 82 and 653 K. Furthermore, the R3-bar->Fm3-barm phase transition does occur in Ba{sub 2}LaIrO{sub 6}, but the transition temperature is found tomore » be much higher than the reported value. - Graphical abstract: Observed (crosses) and calculated (continuous line) profiles of Ba{sub 2}LaIrO{sub 6} at some selected temperature showing the region containing the basic (222), (321) and (400) reflections. Tick marks below indicate the positions of the allowed Bragg's reflections.« less

Mechanical properties and negative thermal expansion of a dense rare earth formate framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Zhanrui; Jiang, Xingxing; Feng, Guoqiang

The fundamental mechanical properties of a dense metal–organic framework material, [NH{sub 2}CHNH{sub 2}][Er(HCOO){sub 4}] (1), have been studied using nanoindentation technique. The results demonstrate that the elastic moduli, hardnesses, and yield stresses on the (021)/(02−1) facets are 29.8/30.2, 1.80/1.83 and 0.93/1.01 GPa, respectively. Moreover, variable-temperature powder and single-crystal X-ray diffraction experiments reveal that framework 1 shows significant negative thermal expansion along its b axis, which can be explained by using a hinge–strut structural motif. - Graphical abstract: The structure of framework, [NH{sub 2}CHNH{sub 2}][Er(HCOO){sub 4}], and its indicatrix of thermal expansion. - Highlights: • The elastic modulus, hardness, and yieldmore » stress properties of a rare earth metal–organic framework material were studied via nanoindentation technique. • Variable-temperature powder X-ray diffraction experiments reveal that this framework shows significant negative thermal expansion along its b axis. • Based on variable-temperature single-crystal X-ray diffraction experiments, the mechanism of negative thermal expansion can be explained by a hinge–strut structural motif.« less

Insight into the biological effects of acupuncture points by X-ray absorption fine structure.

PubMed

Liu, Chenglin; Liu, Qinghua; Zhang, Dongming; Liu, Wei; Yan, Xiaohui; Zhang, Xinyi; Oyanagi, Hiroyuki; Pan, Zhiyun; Hu, Fengchun; Wei, Shiqiang

2018-06-02

Exploration of the biological effects of transition metal ions in acupuncture points is essential to clarify the functional mechanism of acupuncture treatment. Here we show that in the SP6 acupuncture point (Sanyinjiao) the Fe ions are in a high-spin state of approximately t 2g 4.5 e g 1.5 in an Fe-N(O) octahedral crystal field. The Fe K-edge synchrotron radiation X-ray absorption fine structure results reveal that the Fe-N and Fe-O bond lengths in the SP6 acupuncture point are 2.05 and 2.13 Å, respectively, and are 0.05-0.10 Å longer than those in the surrounding tissue. The distorted atomic structure reduces the octahedral symmetry and weakens the crystal field around the Fe ions by approximately 0.3 eV, leading to the high-spin configuration of the Fe ions, which is favorable for strengthening the magnetotransport and oxygen transportation properties in the acupuncture point by the enhanced spin coherence. This finding might provide some insight into the microscopic effect of the atomic and electronic interactions of transition metal ions in the acupuncture point. Graphical Abstract ᅟ.

Study on the solid solution of YMn{sub 1-x}Fe{sub x}O{sub 3}: Structural, magnetic and dielectric properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samal, S.L.; Green, W.; Lofland, S.E.

The solid solution of YMn{sub 1-x}Fe{sub x}O{sub 3} (x=0.0, 0.1, 0.2, 0.3, 0.5, 1.0) was synthesized from the citrate precursor route. The hexagonal crystal structure related to YMnO{sub 3} was stable for x{<=}0.3. Rietveld refinement was carried out on the composition for x=0.3 and was refined to a major hexagonal phase ({approx}97%) with 3% of orthorhombic Y(Fe/Mn)O{sub 3} phase. The a-axis lattice constant increases and the c-axis lattice constant decreases with x for x{<=}0.2. The increase in the c-axis lattice constant at x=0.3 could be due to the doping of significant amount of d{sup 5} ion (high spin Fe{sup 3+}more » ion) in a trigonal bipyramidal crystal field. The detailed structural, magnetic and dielectric properties are discussed. - Graphical abstract: Temperature dependence of {epsilon} of YMn{sub 1-x}Fe{sub x}O{sub 3} (0.0{<=}x{<=}0.3) at 100 kHz. Inset shows the temperature variation of inverse magnetic susceptibility.« less

Prediction and Biochemical Demonstration of a Catabolic Pathway for the Osmoprotectant Proline Betaine

PubMed Central

Kumar, Ritesh; Zhao, Suwen; Vetting, Matthew W.; Wood, B. McKay; Sakai, Ayano; Cho, Kyuil; Solbiati, José; Almo, Steven C.; Sweedler, Jonathan V.; Jacobson, Matthew P.; Gerlt, John A.; Cronan, John E.

2014-01-01

ABSTRACT Through the use of genetic, enzymatic, metabolomic, and structural analyses, we have discovered the catabolic pathway for proline betaine, an osmoprotectant, in Paracoccus denitrificans and Rhodobacter sphaeroides. Genetic and enzymatic analyses showed that several of the key enzymes of the hydroxyproline betaine degradation pathway also function in proline betaine degradation. Metabolomic analyses detected each of the metabolic intermediates of the pathway. The proline betaine catabolic pathway was repressed by osmotic stress and cold stress, and a regulatory transcription factor was identified. We also report crystal structure complexes of the P. denitrificans HpbD hydroxyproline betaine epimerase/proline betaine racemase with l-proline betaine and cis-hydroxyproline betaine. PMID:24520058

Crystal structure details of La- and Bi-substituted hydroxyapatites: Evidence for LaO{sup +} and BiO{sup +} with a very short metal–oxygen bond

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kazin, Pavel E., E-mail: kazin@inorg.chem.msu.ru; Pogosova, Mariam A.; Trusov, Lev A.

Crystal structures of substituted apatites with general formula Ca{sub 10−x}M{sub x}(PO{sub 4}){sub 6}(OH{sub 1−δ}){sub 2−x}O{sub x}, where M=La, Bi, 0≤x<2, were refined using high-resolution X-ray powder diffraction patterns. Individual positions for Ca{sup 2+} and M{sup 3+}-ions localized near Ca2-site were determined. The M{sup 3+}-ion was found shifted toward the hexagonal channel center with respect to the Ca{sup 2+}-ion, forming very short bond with the intrachannel O{sup 2−}, while leaving considerably longer distances to other oxygen atoms, which suggested the existence of a MO{sup +} ion. Distinct bands of stretching M–O modes were observed in the Raman and FT-IR spectra ofmore » the compounds. The bond lengths for BiO{sup +} and LaO{sup +} were estimated to be 2.05(1) and 2.09(1) Å correspondingly. The latter was almost 0.3 Å lower than the shortest La–O bond in La{sub 2}O{sub 3}. The realization of such a strong lanthanide–oxygen bond in a crystal lattice could provide a very high axial ligand field and might be implemented to develop high-energy-barrier single-molecule magnets as well as to tune properties of lanthanide-based luminophores. - Graphical abstract: A fragment of the La-for-Ca substituted apatite crystal structure focusing on the La–O bond. - Highlights: • Individual positions in the apatite crystal lattice for a doping atom (La, Bi) and Ca. • The doping atom shifts toward the center of the hexagonal channel. • BiO{sup +} and LaO{sup +} with estimated short bond lengths of 2.05 and 2.09 Å respectively.« less

Multi Resonance Shear Mode Transducers

DTIC Science & Technology

2016-11-21

burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing...ABSTRACT Crystallographic engineering of single crystal relaxor-based ferroelectrics was used to design broadband, compact, high power, low frequency...using multiple d36 crystal geometries or combinations of d36 and other crystal cuts. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17

Er{sub 1.33}Pt{sub 3}Ga{sub 8}: A modulated variant of the Er{sub 4}Pt{sub 9}Al{sub 24}-structure type

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oswald, Iain W.H.; Gourdon, Olivier; Bekins, Amy

Single crystals of Er{sub 1.33}Pt{sub 3}Ga{sub 8} were synthesized in a molten Ga flux. Er{sub 1.33}Pt{sub 3}Ga{sub 8} can be considered to be a modulated variant of the Er{sub 4}Pt{sub 9}Al{sub 24}-structure type, where the partial occupancies are ordered. Indeed, the presence of weak satellite reflections indicates a complex organization and distribution of the Er and Ga atoms within the [ErGa] slabs. The structure has been solved based on single crystal X-ray diffraction data in the monoclinic superspace group X2/m(0β0)00 with a commensurate modulated vector q=1/3b*. Precession images also indicate diffusion in the perpendicular direction indicating a partial disorder ofmore » this arrangement from layer to layer. In addition, Er{sub 1.33}Pt{sub 3}Ga{sub 8} shows antiferromagnetic ordering at T{sub N}~5 K. - Graphical abstract: A precession image of the hk0 zone showing weak, periodic, unindexed reflections indicating modulation and representation of the commensurate [ErGa] layer showing the waving modulated occupation. - Highlights: • Single crystals of Er{sub 1.33}Pt{sub 3}Ga{sub 8} were grown from gallium flux. • The structure of Er{sub 1.33}Pt{sub 3}Ga{sub 8} is compared to Er{sub 4}Pt{sub 9}Al{sub 24}. • Structure has been solved in the monoclinic superspace group X2/m(0β0)00 with a commensurate modulated vector q=1/3b*.« less

The new silver borate Ag{sub 3}B{sub 5}O{sub 9}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sohr, Gerhard; Falkowski, Viktoria; Huppertz, Hubert, E-mail: hubert.huppertz@uibk.ac.at

2015-05-15

Single crystals of Ag{sub 3}B{sub 5}O{sub 9} were obtained via high-pressure synthesis at 3 GPa and 600 °C, using a Walker-type multianvil high-pressure device. Ag{sub 3}B{sub 5}O{sub 9} crystalizes with a=674.7(2), b=943.5(2), c=1103.5(2) pm, V=0.7025(2) nm{sup 3}, and Z=4 in the noncentrosymmetric space group P2{sub 1}2{sub 1}2{sub 1} (no. 19). The orthorhombic structure was refined from 3740 independent reflections with R1=0.0496 and wR2=0.587 (all data). It is built up from infinite corner-sharing chains of BO{sub 4} tetrahedra along the a axis, which are interconnected by BO{sub 3} groups to form a network. In the structure, three crystallographically independent sites aremore » occupied with Ag{sup +} cations exhibiting argentophillic interactions. The synthetic conditions as well as the results of the single crystal structure analysis are presented. - Graphical abstract: Noncentrosymmetric silver borate: During investigations in the system Ag–B–O, a new noncentrosymmetric silver borate Ag{sub 3}B{sub 5}O{sub 9} was discovered. The new structure type is built up from corner-sharing BO{sub 3} and BO{sub 4} groups, forming a network. Argentophillic interactions are clearly indicated by the Ag{sup +}⋯Ag{sup +} distances present in the structure. - Highlights: • A noncentrosymmetric borate Ag{sub 3}B{sub 5}O{sub 9} is accessible via high-pressure synthesis. • Ag{sub 3}B{sub 5}O{sub 9} is the second high-pressure silver borate. • Ag{sup +}⋯Ag{sup +} distances in Ag3B5O9 clearly indicate the presence of argentophillic interactions.« less

Effects of Co contents on the microstructures and properties of the electrodeposited NiCo–Zr composite coatings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Fei; Jiang, Chuanhai, E-mail: chuanhaijiang1963@163.com; Zhao, Yuantao

2015-05-15

Highlights: • The novel NiCo–Zr coatings were prepared by electro-deposition. • Surface morphology, crystal structure, grain size and microstrain were examined. • Texture, residual stress and corrosion resistance were investigated. • Addition of Co increased the hardness and corrosion resistance of the coatings. - Abstract: In this study, the NiCo–Zr composite coatings were prepared from the electrolytes with different Co{sup 2+} concentrations by electrodeposition method. The effects of Co contents on the crystal structure, surface morphology, grain size, microstrain and residual stress were examined by X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), Energy dispersive X-ray spectroscopy (EDX) andmore » atomic force microscope (AFM). The corrosion resistance of the composite coatings was also examined by the potentiodynamic polarization and electrochemical impedance (EIS) measurements. The results revealed that the crystal structures of the coatings were dependent on the Co contents and addition of Co content of 58 wt% resulted in the formation of hexagonal (hcp) Co. The increasing Co contents in the NiCo–Zr composite coatings resulted in the smoother and more compact surface, decreased the grain size and increased the microstrain. The micro-hardness and residual stress also increased with increasing Co contents. The addition of Co increased the corrosion resistance of the NiCo–Zr composite coatings compared with the Ni–Zr coating while the corrosion resistance of the NiCo–Zr composite coatings decreased as the Co contents increased.« less

Synthesis, crystal structure and magnetic properties of the two polymorphs of novel S=1 osmate; Li{sub 4}MgOsO{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Phoung-Hieu T.; Kemei, Moureen C.; Tan, Malinda S.

2016-10-15

Li{sub 4}MgOsO{sub 6} was synthesized by two different solid-state reaction procedures. The crystal structures were determined by X-ray powder diffraction technique and it was revealed that Li{sub 4}MgOsO{sub 6} crystallizes in two different crystal symmetries in ordered rock salt structure type, namely monoclinic C2/m and orthorhombic Fddd. The unit cell constants for the monoclinic system are a=5.1074(4) Å, b=8.8182(4) Å, c=5.0902(2) Å, and β=109.845(4)° and those of the orthorhombic structure are a=5.8485(1) Å, b=8.3821(1) Å, and c=17.6212(3) Å. In both systems, Os{sup 6+} ions reside exclusively in a specific crystallographic position while Li{sup +} and Mg{sup 2+} ions exhibit mixmore » occupancy. The temperature dependent magnetic susceptibility data for both S=1 osmate systems do not support the occurrence of any magnetic transition down to 2 K. The Curie–Weiss fit to the paramagnetic regime of the magnetic susceptibility data reveal highly negative θ value (−114.81 K and −121.87 K for C2/m and for Fddd systems, respectively), which are indicative of predominant antiferromagnetic (AFM) interactions in both systems. The experimental effective magnetic moment (μ{sub eff}) value for the monoclinic phase is 2.13 μB and that of the orthorhombic system is 2.34 μB. Due to the rather strong AFM interactions and lack of magnetic transition down to 2 K, both of these novel osmates are placed in the class of highly frustrated magnets. Low temperature magnetic susceptibility (below 2 K) and dynamic magnetic properties studies (μsr studies) are in order to better understand the magnetic ground states of these two polymorphs of Li{sub 4}MgOsO{sub 6}. - Graphical abstract: The structural transformation between two modifications of highly frustrated Li{sub 4}MgOsO{sub 6}. - Highlights: • Li4MgOsO{sub 6} was synthesized in two different crystal systems. • The monoclinic variant crystallizes in C2/m space group, while the orthorhombic version forms in Fddd space group. • The Os{sup 6+} ions are fully ordered while Li{sup +} and Mg{sup 2+} are mixed occupied. • These systems are the first Os{sup 6+} compounds in ordered NaCl structure type. • Both compounds exhibit high degree of geometric magnetic frustration.« less

Synthesis, crystal structure, and ionic conductivity of a new layered metal phosphate, Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Sung-Chul; Kwak, Hyun-Jung; Yoo, Chung-Yul

2016-11-15

A new layered metal phosphate, Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}, was synthesized in the form of either a single-crystal or polycrystalline powder using the molten hydroxide flux method or a solid-state reaction, respectively. Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} crystallizes to the P2{sub 1}/n (Z=4) monoclinic space group with lattice parameters a≈4.95 Å, b≈22.06 Å, c≈8.63 Å, and β≈91.5°. The structure is composed of stacked [LiSrAl(PO{sub 4}){sub 2}] layers alternating regularly with [LiSrPO{sub 4}] layers. In the [LiSrAl(PO{sub 4}){sub 2}] sublattice, the AlO{sub 6} octahedra and PO{sub 4} tetrahedra are tilted cooperatively to form an anionic, corrugated, two-dimensional [Al(PO{sub 4}){sub 2}]{supmore » 3−} framework that can be regarded as a “distorted-glaserite” structure. The [LiSrPO{sub 4}] sublattice is that of a layered block containing a six-membered ring formed from alternating linkages of LiO{sub 4} and PO{sub 4} tetrahedra. The six-membered rings show a boat-type arrangement with the up(U) or down(D) pointing sequence, UUDUUD. The interspace between the two sublattices generates a two-dimensional pathway for Li{sup +} ion conduction. The impedance measurement indicated that Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} had a moderate ion conductivity (σ≈1.30×10{sup −4} S cm{sup −1} at 667 K), with an activation energy E{sub a}≈1.02 eV. - Graphical abstract: Polyhedral view of Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3}. Li{sup +} ions are represented by green spheres, Sr atoms by white spheres, AlO{sub 6} groups by octahedra, and PO{sub 4} groups by tetrahedra. - Highlights: • New compound Li{sub 2}Sr{sub 2}Al(PO{sub 4}){sub 3} is reported. • The crystal structure is investigated by single-crystal XRD analysis. • The structure is formed by the alternate stacking of two different sublattices. • Correlation between the crystal structure and ionic conductivity is discussed.« less

Concerted Interconversion between Ionic Lock Substates of the β2 Adrenergic Receptor Revealed by Microsecond Timescale Molecular Dynamics

PubMed Central

Romo, Tod D.; Grossfield, Alan; Pitman, Michael C.

2010-01-01

Abstract The recently solved crystallographic structures for the A2A adenosine receptor and the β1 and β2 adrenergic receptors have shown important differences between members of the class-A G-protein-coupled receptors and their archetypal model, rhodopsin, such as the apparent breaking of the ionic lock that stabilizes the inactive structure. Here, we characterize a 1.02 μs all-atom simulation of an apo-β2 adrenergic receptor that is missing the third intracellular loop to better understand the inactive structure. Although we find that the structure is remarkably rigid, there is a rapid influx of water into the core of the protein, as well as a slight expansion of the molecule relative to the crystal structure. In contrast to the x-ray crystal structures, the ionic lock rapidly reforms, although we see an activation-precursor-like event wherein the ionic lock opens for ∼200 ns, accompanied by movements in the transmembrane helices associated with activation. When the lock reforms, we see the structure return to its inactive conformation. We also find that the ionic lock exists in three states: closed (or locked), semi-open with a bridging water molecule, and open. The interconversion of these states involves the concerted motion of the entire protein. We characterize these states and the concerted motion underlying their interconversion. These findings may help elucidate the connection between key local events and the associated global structural changes during activation. PMID:20074514

The Biological Macromolecule Crystallization Database and NASA Protein Crystal Growth Archive

PubMed Central

Gilliland, Gary L.; Tung, Michael; Ladner, Jane

1996-01-01

The NIST/NASA/CARB Biological Macromolecule Crystallization Database (BMCD), NIST Standard Reference Database 21, contains crystal data and crystallization conditions for biological macromolecules. The database entries include data abstracted from published crystallographic reports. Each entry consists of information describing the biological macromolecule crystallized and crystal data and the crystallization conditions for each crystal form. The BMCD serves as the NASA Protein Crystal Growth Archive in that it contains protocols and results of crystallization experiments undertaken in microgravity (space). These database entries report the results, whether successful or not, from NASA-sponsored protein crystal growth experiments in microgravity and from microgravity crystallization studies sponsored by other international organizations. The BMCD was designed as a tool to assist x-ray crystallographers in the development of protocols to crystallize biological macromolecules, those that have previously been crystallized, and those that have not been crystallized. PMID:11542472

Molten salt flux synthesis and crystal structure of a new open-framework uranyl phosphate Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}: Spectroscopic characterization and cationic mobility studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yagoubi, S., E-mail: said.yagoubi@cea.fr; Renard, C.; Abraham, F.

2013-04-15

The reaction of triuranyl diphosphate tetrahydrate precursor (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} with a CsI flux at 750 °C yields a yellow single crystals of new compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. The crystal structure (monoclinic, space group C2/c, a=13.6261 (13) Å, b=8.1081(8) Å, c=12.3983(12) Å, β=114.61(12)°, V=1245.41(20) Å{sup 3} with Z=4) has been solved using direct methods and Fourier difference techniques. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R1=0.028 and wR2=0.071 for 79 parameters and 1352 independent reflections with I≥2σ(I) collected on a BRUKER AXS diffractometer with MoKα radiation and a charge-coupledmore » device detector. The crystal structure is built by two independent uranium atoms in square bipyramidal coordination, connected by two opposite corners to form infinite chains {sup 1}{sub ∞}[UO{sub 5}] and by one phosphorus atom in a tetrahedral environment PO{sub 4}. The two last entities {sup 1}{sub ∞}[UO{sub 5}] and PO{sub 4} are linked by sharing corners to form a three-dimensional structure presenting different types of channels occupied by Cs{sup +} alkaline cations. Their mobility within the tunnels were studied between 280 and 800 °C and compared with other tunneled uranyl minerals. The infrared spectrum shows a good agreement with the values inferred from the single crystal structure analysis of uranyl phosphate compound. - Graphical abstract: Arrhenius plot of the electrical conductivity of tunneled compounds Cs{sub 3}U{sub 2}PO{sub 10} and CsU{sub 2}Nb{sub 2}O{sub 11.5}. Highlights: ► The reaction of (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} in excess of molten CsI leads to single-crystals of new tunneled compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. ► Ionic conductivity measurements and crystal structure analysis indicate a strong connection of the Cs{sup +} cations to the tunnels. ► A low symmetry in Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2} is the cause of IR activation and splitting of the bands in the IR spectrum.« less

Synthesis and structural characterization of the Zintl phases Na{sub 3}Ca{sub 3}TrPn{sub 4}, Na{sub 3}Sr{sub 3}TrPn{sub 4}, and Na{sub 3}Eu{sub 3}TrPn{sub 4} (Tr=Al, Ga, In; Pn=P, As, Sb)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yi; Suen, Nian-Tzu; College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002

15 new quaternary Zintl phases have been synthesized by solid-state reactions from the respective elements, and their structures have been determined by single-crystal X-ray diffraction. Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) crystallize in the hexagonal crystal system with the non-centrosymmetric space group P6{sub 3}mc (No. 186). The structure represents a variant of the K{sub 6}HgS{sub 4} structure type (Pearson index hP22) and features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. The nominal formula rationalization [Na{sup +}]{sub 3}[E{sup 2+}]{sub 3}[TrPn{sub 4}]{sup 9–} follows themore » octet rule, suggesting closed-shell configurations for all atoms and intrinsic semiconducting behavior. However, structure refinements for several members hint at disorder and mixing of cations that potentially counteract the optimal valence electron count. - Graphical abstract: The hexagonal, non-centrosymmetric structure of Na{sub 3}E{sub 3}TrPn{sub 4} (E=Ca, Sr, Eu; Tr=Al, Ga, In; Pn=P, As, Sb) features [TrPn{sub 4}]{sup 9–} tetrahedral units, surrounded by Na{sup +} and Ca{sup 2+}, Sr{sup 2+}, Eu{sup 2+} cations. - Highlights: • 15 quaternary phosphides, arsenides, and antimonides are synthesized and structurally characterized. • The structure is a variant of the hexagonal K{sub 6}HgS{sub 4}-type, with distinctive pattern for the cations. • Occupational and/or positional disorder of yet unknown origin exists for some members of the series.« less

CORROSION RESISTANT ZEOLITE COATINGS BY IN-SITU CRYSTALLIZATION. (R828134)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Ammonium–cobalt–nickel phosphates, NH{sub 4}[Co{sub 1−x}Ni{sub x}PO{sub 4}]·H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Torre-Fernández, Laura; Trobajo, Camino; Pedro, Imanol de

The ammonium–cobalt–nickel phosphates, NH{sub 4}[Co{sub 1−x}Ni{sub x}PO{sub 4}]·H{sub 2}O (x=0.00, 0.34, 0.59, 0.70, 1.00), and the deuterated forms, ND{sub 4}[Co{sub 1−x}Ni{sub x}PO{sub 4}]·D{sub 2}O (x=0.00, 0.38, 0.48, 0.69, 0.85), have been synthesized under mild hydrothermal conditions and characterised using X-ray and neutron diffraction, chemical and thermal analysis, and magnetic measurements. Their crystal structures, including hydrogen positions, were determined by Rietveld refinement using single-crystal X-ray and neutron powder diffraction data. The space group of these orthorhombic crystals modifies as a function of their composition. The magnetic susceptibility and magnetization measurements of these ammonium–cobalt–nickel phosphates show antiferromagnetic behaviour, and the Neel temperaturemore » evolves from 5.5 K (x=0.00) up to 13.2 K (x=1.00). - Graphical abstract: We obtained single crystals for all the members of the family. In this series, although all crystals are orthorhombic, the space group changes as a function of the composition, showing how the single-crystal diffraction data is capable to manifest structural subtleties that had not been described before for this group of materials. All the investigated materials behave antiferromagnetically with ordering temperatures from 5.5 K up to 13.2 K. Display Omitted - Highlights: • The ammonium–cobalt–nickel phosphates, NH{sub 4}[Co{sub 1−x}Ni{sub x}PO{sub 4}]·H{sub 2}O (x=0.00, 0.34, 0.59, 0.70, 1.00) and the deuterated forms ND4[Co1-xNixPO4]·D{sub 2}O (x=0.00, 0.38, 0.49, 0.68, 0.85) have synthesized by hydrothermal synthesis. • The structural studies of these compounds are introduced as a function of the composition. • The magnetic studies show an antiferromagnetically behavior with ordering temperatures from 5.5 K to 13.2 K.« less

Fluorine sites in glasses and transparent glass-ceramics of the system Na{sub 2}O/K{sub 2}O/Al{sub 2}O{sub 3}/SiO{sub 2}/BaF{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bocker, Christian, E-mail: christian.bocker@uni-jena.d; Munoz, Francisco; Duran, Alicia

2011-02-15

The transparent glass-ceramics obtained in the silicate system Na{sub 2}O/K{sub 2}O/SiO{sub 2}/BaF{sub 2} show homogeneously dispersed BaF{sub 2} nano crystals with a narrow size distribution. The X-ray diffraction and the nuclear magnetic resonance spectroscopy were applied to glasses and the respective glass-ceramics in order to clarify the crystallization mechanism and the role of fluorine during crystallization. With an increasing annealing time, the concentration and also the number of crystals remain approximately constant. With an increasing annealing temperature, the crystalline fraction increases until a saturation limit is reached, while the number of crystals decreases and the size of the crystals increases.more » Fluoride in the glassy network occurs as Al-F-Ba, Al-F-Na and also as Ba-F structures. The latter are transformed into crystalline BaF{sub 2} and fluoride is removed from the Al-F-Ba/Na bonds. However, some fluorine is still present in the glassy phase after the crystallization. -- Graphical abstract: The X-ray diffraction and the nuclear magnetic resonance spectroscopy were applied to glasses in the silicate system Na{sub 2}O/K{sub 2}O/SiO{sub 2}/BaF{sub 2} and the respective glass-ceramics with BaF{sub 2} nano crystals in order to clarify the crystallization mechanism and the role of fluorine during crystallization. Display Omitted Research highlights: {yields} BaF{sub 2} nano crystals are precipitated from a silicate glass system. {yields} Ostwald ripening during the late stage of crystallization does not occur. {yields} Fluorine in the glass is coordinated with Ba as well as Al together with Ba or Na.{yields} In the glass-ceramics, the residual fluorine is coordinated as Al-F-Ba/Na.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zare, Bijan; Faramarzi, Mohammad Ali; Sepehrizadeh, Zargham

Highlights: ► Biosynthesis of rod shape tellurium nanoparticles with a hexagonal crystal structure. ► Extraction procedure for isolation of tellurium nanoparticles from Bacillus sp. BZ. ► Extracted tellurium nanoparticles have good bactericidal activity against some bacteria. -- Abstract: In this study, a tellurium-transforming Bacillus sp. BZ was isolated from the Caspian Sea in northern Iran. The isolate was identified by various tests and 16S rDNA analysis, and then used to prepare elemental tellurium nanoparticles. The isolate was subsequently used for the intracellular biosynthesis of elemental tellurium nanoparticles. The biogenic nanoparticles were released by liquid nitrogen and purified by an n-octylmore » alcohol water extraction system. The shape, size, and composition of the extracted nanoparticles were characterized. The transmission electron micrograph showed rod-shaped nanoparticles with dimensions of about 20 nm × 180 nm. The energy dispersive X-ray and X-ray diffraction spectra respectively demonstrated that the extracted nanoparticles consisted of only tellurium and have a hexagonal crystal structure. This is the first study to demonstrate a biological method for synthesizing rod-shaped elemental tellurium by a Bacillus sp., its extraction and its antibacterial activity against different clinical isolates.« less

Supercritical-assistant liquid crystal template approach to synthesize mesoporous titania/multiwalled carbon nanotube composites with high visible-light driven photocatalytic performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Chen; Li, Youji, E-mail: bcclyj@163.com; Xu, Peng

2014-12-15

Graphical abstract: We investigate the influence of mesoporous titania content upon the visible-light driven photocatalytic performance of MPT/MWCNTs in phenol degradation. - Highlights: • MPT/MWCNTs were fabricated by liquid-crystal template in supercritical CO{sub 2}. • MPT/MWCNTs show high visible-light driven photoactivity for phenol degradation. • MPT/MWCNTs also show high reusable photoactivity under visible irradiation. • MPT content can control visible-light driven photoactivity of MPT/MWCNTs. • MPT is not easily broken away from from MPT/MWCNT composites. - Abstract: Mesoporous titania (MPT) was deposited onto multiwalled carbon nanotubes (MWCNTs) by deposition of titanium sol containing liquid-crystal template with assistant of supercritical CO{submore » 2}. The products were characterized with various analytical techniques to determine their structural, morphological, optical absorption and photocatalytic properties. The results indicate that in photocatalytic degradation of phenol under visible light, the mixtures or composites of MPT and MWCNT show the high efficiency because of synergies between absorbing visible light, releasing electrons and facilitating transfer of charge carriers of MWCNTs and providing activated centers of MPT. Because of the mutual constraint between MPT and MWCNTs on the photocatalytic efficiency, the optimal loading of MPT in MPT/MWCNT-3 for phenol degradation is 48%. Because the intimate contact between MWCNTs and MPT is more beneficial to electron transformation, photoactivity of mixture is lower than that of composites with high reusable performance. The optimum conditions of phenol degradation were obtained.« less

Novel ethylenediamine-gallium phosphate containing 6-fold coordinated gallium atoms with unusual four equatorial Ga–N bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Torre-Fernández, Laura; Espina, Aránzazu; Khainakov, Sergei A.

2014-07-01

A novel ethylenediamine-gallium phosphate, formulated as Ga(H{sub 2}NCH{sub 2}CH{sub 2}NH{sub 2}){sub 2}PO{sub 4}·2H{sub 2}O, was synthesized under hydrothermal conditions. The crystal structure, including hydrogen positions, was determined using single-crystal X-ray diffraction data (monoclinic, a=9.4886(3) Å, b=6.0374(2) Å, c=10.2874(3) Å, and β=104.226(3)°, space group Pc) and the bulk was characterized by chemical (Ga–P–C–H–N) and thermal analysis (TG–MS and DSC), including activation energy data of its thermo-oxidative degradation, powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (SS-NMR) measurements, and transmission electron microscopy (TEM, SAED/NBD, and STEM BF-EDX). The crystal structure is built up of infinite zig-zag chains running along the c-axis, formedmore » by vertex-shared (PO{sub 4}) and (GaO{sub 2}N{sub 4}) polyhedra. The new compound is characterized by unusual four equatorial Ga–N bonds coming from two nonequivalent ethylenediamine molecules and exhibits strong blue emission at 430 nm (λ{sub ex}=350 nm) in the solid state at room temperature. - Graphical abstract: Single crystals of a new ethylenediamine-gallium phosphate, Ga(H{sub 2}NCH{sub 2}CH{sub 2}NH{sub 2}){sub 2}PO{sub 4}·2H{sub 2}O, were obtained and the structural features presented. This structure is one of the scarce examples of GaPO with Ga–N bonds reported. - Highlights: • A novel ethylenediamine-gallium phosphate was hydrothermally synthesized. • The new compound is characterized by unusual four equatorial Ga–N bonds. • Void-volume analysis shows cages and channels with sizes ideally suited to accommodate small molecules. • The new compound exhibits strong blue emission.« less

Synthesis, crystal structure, and photocatalytic activity of a new two-layer Ruddlesden-Popper phase, Li{sub 2}CaTa{sub 2}O{sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang Zhenhua; Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026; Tang Kaibin

2008-04-15

A new two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} has been synthesized for the first time. The detailed structure determination of Li{sub 2}CaTa{sub 2}O{sub 7} performed by powder X-ray diffraction (XRD) and electron microscopy (ED) shows that it crystallizes in the space group Fmmm [a{approx}5.5153(1), b{approx}5.4646(1), c{approx}18.2375(3)A]. UV-visible diffuse reflection spectrum of the prepared Li{sub 2}CaTa{sub 2}O{sub 7} indicates that it had absorption in the UV region. The photocatalytic activity of the Li{sub 2}CaTa{sub 2}O{sub 7} powders was evaluated by degradation of RhB molecules in water under ultra visible light irradiation. The results showed that Li{sub 2}CaTa{sub 2}O{sub 7} hasmore » high photocatalytic activity at room temperature. Therefore, the preparation and properties studies of Li{sub 2}CaTa{sub 2}O{sub 7} with a two-layer Ruddlesden-Popper structure suggest potential future applications in photocatalysis. - Graphical abstract: Crystal structure of a two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} A new two-layer Ruddlesden-Popper phase Li{sub 2}CaTa{sub 2}O{sub 7} has been synthesized for the first time. Li{sub 2}CaTa{sub 2}O{sub 7} crystallizes in the space group Fmmm determined by powder X-ray and electron diffraction. UV-visible diffuse reflection spectra and the photocatalytic degradation of RhB molecules in water under ultra visible light irradiation show that Li{sub 2}CaTa{sub 2}O{sub 7} is a potential material in photocatalysis.« less

Structural analysis of the intracellular domain of (pro)renin receptor fused to maltose-binding protein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yanfeng; Gao, Xiaoli; Michael Garavito, R., E-mail: garavito@msu.edu

2011-04-22

Highlights: {yields} Crystal structure of the intracellular domain of (pro)renin receptor (PRR-IC) as MBP fusion protein at 2.0 A (maltose-free) and 2.15 A (maltose-bound). {yields} MBP fusion protein is a dimer in crystals in the presence and absence of maltose. {yields} PRR-IC domain is responsible for the dimerization of the fusion protein. {yields} Residues in the PRR-IC domain, particularly two tyrosines, dominate the intermolecular interactions, suggesting a role for the PRR-IC domain in PRR dimerization. -- Abstract: The (pro)renin receptor (PRR) is an important component of the renin-angiotensin system (RAS), which regulates blood pressure and cardiovascular function. The integral membranemore » protein PRR contains a large extracellular domain ({approx}310 amino acids), a single transmembrane domain ({approx}20 amino acids) and an intracellular domain ({approx}19 amino acids). Although short, the intracellular (IC) domain of the PRR has functionally important roles in a number of signal transduction pathways activated by (pro)renin binding. Meanwhile, together with the transmembrane domain and a small portion of the extracellular domain ({approx}30 amino acids), the IC domain is also involved in assembly of V{sub 0} portion of the vacuolar proton-translocating ATPase (V-ATPase). To better understand structural and multifunctional roles of the PRR-IC, we report the crystal structure of the PRR-IC domain as maltose-binding protein (MBP) fusion proteins at 2.0 A (maltose-free) and 2.15 A (maltose-bound). In the two separate crystal forms having significantly different unit-cell dimensions and molecular packing, MBP-PRR-IC fusion protein was found to be a dimer, which is different with the natural monomer of native MBP. The PRR-IC domain appears as a relatively flexible loop and is responsible for the dimerization of MBP fusion protein. Residues in the PRR-IC domain, particularly two tyrosines, dominate the intermonomer interactions, suggesting a role for the PRR-IC domain in protein oligomerization.« less

Growth and characterization of diammonium copper disulphate hexahydrate single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siva Sankari, R.; Perumal, Rajesh Narayana, E-mail: r.shankarisai@gmail.com

2014-03-01

Graphical abstract: Diammonium copper disulphate hexahydrate (DACS) is one of the most promising inorganic dielectric crystals with exceptional mechanical properties. Good quality crystals of DACS were grown by using solution method in a period of 30 days. The grown crystals were subjected to single crystal X-ray diffraction analysis in order to establish their crystalline nature. Thermo gravimetric, differential thermal analysis, FTIR, and UV–vis–NIR analysis were performed for the crystal. Several solid state physical parameters have been determined for the grown crystals. The dielectric constant and the dielectric loss and AC conductivity of the grown crystal were studied as a functionmore » of frequency and temperature has been calculated and plotted. - Highlights: • Diammonium copper disulphate is grown for the first time and CCDC number obtained. • Thermal analysis is done to see the stability range of the crystals. • Band gap and UV cut off wavelength of the crystal are determined to be 2.4 eV and 472.86 nm, respectively. • Dielectric constant, dielectric loss and AC conductivity are plotted as a function of applied field. - Abstract: Diammonium copper disulphate hexahydrate is one of the most promising inorganic crystals with exceptional dielectric properties. A good quality crystal was harvested in a 30-day period using solution growth method. The grown crystal was subjected to various characterization techniques like single crystal X-ray diffraction analysis, thermo gravimetric, differential thermal analysis, FTIR, and UV–vis–NIR analysis. Unit cell dimensions of the grown crystal have been identified from XRD studies. Functional groups of the title compounds have been identified from FTIR studies. Thermal stability of the samples was checked by TG/DTA studies. Band gap of the crystal was calculated. The dielectric constant and dielectric loss were studied as a function of frequency of the applied field. AC conductivity was plotted as a function of temperature.« less

[La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] the first lanthanum uranyl-vanadate with structure built from two types of sheets based upon the uranophane anion-topology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mer, A.; Obbade, S.; Rivenet, M.

2012-01-15

The new lanthanum uranyl vanadate divanadate, [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})] was obtained by reaction at 800 Degree-Sign C between lanthanum chloride, uranium oxide (U{sub 3}O{sub 8}) and vanadium oxide (V{sub 2}O{sub 5}) and the structure was determined from single-crystal X-ray diffraction data. This compound crystallizes in the orthorhombic system with space group P2{sub 1}2{sub 1}2{sub 1} and unit-cell parameters a=6.9470(2) A, b=7.0934(2) A, c=25.7464(6) A, V=1268.73(5) A{sup 3}, Z=4. A full matrix least-squares refinement yielded R{sub 1}=0.0219 for 5493 independent reflections. The crystal structure is characterized by the stacking of uranophane-type sheets {sup 2}{sub {infinity}}[(UO{sub 2})(VO{sub 4})]{sup -}more » and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +} connected through La-O bonds involving the uranyl oxygen of the uranyl-vanadate sheets. The double layers result from the connection of two {sup 2}{sub {infinity}}[La(UO{sub 2})(VO{sub 4}){sub 2}]{sup -} sheets derived from the uranophane anion-topology by replacing half of the uranyl ions by lanthanum atoms and connected through the formation of divanadate entities. - Graphical abstract: A view of the three-dimensional structure of [La(UO{sub 2})V{sub 2}O{sub 7}][(UO{sub 2})(VO{sub 4})]. Highlights: Black-Right-Pointing-Pointer New lanthanum uranyl vanadate divanadate has been synthesized. Black-Right-Pointing-Pointer Structure was determined from single-crystal X-ray diffraction data. Black-Right-Pointing-Pointer Structure is characterized by uranophane-type sheets and double layers {sup 2}{sub {infinity}}[La(UO{sub 2})(V{sub 2}O{sub 7})]{sup +}.« less

Synthesis, structure and optical properties of two isotypic crystals, Na{sub 3}MO{sub 4}Cl (M=W, Mo)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Shujuan; Bai, Chunyan; Zhang, Bingbing

Two isotypic compounds, Na{sub 3}MO{sub 4}Cl (M = W, Mo) have been obtained from the high temperature solution, and their structures were determined by single-crystal X-ray diffraction. Both of them crystallize in the space group P4/nmm of tetragonal system with the unit cells: a=7.5181(15), c=5.360(2) for Na{sub 3}WO{sub 4}Cl and a=7.4942(12), c=5.3409(18) for Na{sub 3}MoO{sub 4}Cl. The structure exhibits a 3D network built up by the ClNa{sub 6} groups, and the MO{sub 4} groups reside in the tunnels of the 3D network. The structural similarities and differences between Na{sub 3}MO{sub 4}Cl (M=W, Mo) and Sr{sub 3}MO{sub 4}F (M=Al, Ga) havemore » been discussed. Meanwhile, detailed structure comparison analyses between Na{sub 3}MO{sub 4}Cl (M=W, Mo) and Na{sub 3}MO{sub 4}F (M=W, Mo) indicate that the different connection modes of ClNa{sub 6} and FNa{sub 6} make Na{sub 3}MO{sub 4}Cl and Na{sub 3}MO{sub 4}F crystallize in different structures. The IR spectra were used to verify the validity of the structure. The diffuse reflectance spectra show that the UV absorption edges are about 249 nm (4.99 eV) and 265 nm (4.69 eV) for Na{sub 3}WO{sub 4}Cl and Na{sub 3}MoO{sub 4}Cl, respectively. In addition, the first-principles theoretical studies are also carried out to aid the understanding of electronic structures and linear optical properties. - Graphical abstract: Two isotypic compounds, Na{sub 3}MO{sub 4}Cl (M=W, Mo) have been obtained from the high temperature solution. Both of them crystallize in the space group P4/nmm of tetragonal system. The structure exhibits a 3D network built up by the ClNa{sub 6} groups, and the MO{sub 4} groups reside in the tunnels of the 3D network. - Highlights: • Structure and properties of Na{sub 3}MO{sub 4}Cl (M=W, Mo) are reported for the first time. • They show a 3D network built by ClNa{sub 6}, and WO{sub 4} lies in the tunnels of the network. • IR spectra were used to verify the validity of the structure. • Band structures and density of states have been calculated.« less

Structural and dielectric properties of A(Fe{sub 1/2}Ta{sub 1/2})O{sub 3} [A = Ba, Sr, Ca

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Alo; Sinha, T.P., E-mail: sinha_tp@yahoo.com

2011-04-15

Graphical abstract: FTIR spectra of BFT, SFT and CFT at room temperature. Research highlights: {yields} The structural and dielectric properties of BaFe{sub 1/2}Ta{sub 1/2}O{sub 3}, SrFe{sub 1/2}Ta{sub 1/2}O{sub 3} and CaFe{sub 1/2}Ta{sub 1/2}O{sub 3}. {yields} Fourier transform infrared spectra show two primary phonon modes of the samples at around 450 cm{sup -1} and 620 cm{sup -1}. {yields} The compounds show significant frequency dispersion in its dielectric properties. {yields} The relaxation mechanism of the samples is modelled by Cole-Cole equation. -- Abstract: The complex perovskite oxide barium iron tantalate (BFT), BaFe{sub 1/2}Ta{sub 1/2}O{sub 3}, strontium iron tantalate (SFT), SrFe{sub 1/2}Ta{sub 1/2}O{submore » 3} and calcium iron tantalate (CFT), CaFe{sub 1/2}Ta{sub 1/2}O{sub 3} are synthesized by a solid-state reaction technique. Rietveld refinement of the X-ray diffraction data of the samples shows that BFT and SFT crystallize in cubic structure, with lattice parameter a = 4.06 A for BFT and 3.959 A for SFT, whereas CFT crystallizes in orthorhombic structure having lattice parameters a = 5.443 A, b = 5.542 A and c = 7.757 A. Fourier transform infrared spectra show two primary phonon modes of the samples at around 450 cm{sup -1} and 620 cm{sup -1}. The compounds show significant frequency dispersion in its dielectric properties. The complex impedance plane plots of the samples show that the relaxation (conduction) mechanism in these materials is purely a bulk effect arising from the semiconductive grains. The relaxation mechanism of the samples is modelled by Cole-Cole equation. The frequency dependent conductivity spectra are found to follow the power law.« less

Technical Operations Support III (TOPS III). Task Order 0018: Nanostructured Graphene-Like Polymers

DTIC Science & Technology

2010-06-01

diverse response by a large class of materials: viscoelastic fluids, inelasticity, crystallization of polymers, twinning, shape memory alloys , single...crystal super alloys , and viscoelastic solids. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT: SAR 18. NUMBER...twinning (Rajagopal and Srinivasa (1997)), Kannan et al. (2002)), shape memory alloys (Rajagopal and Srinivasa (1999)), single crystal super alloys

Observation of Spectral Diffusion in Crystals Using Single Impurity Molecules

DTIC Science & Technology

1990-10-31

from 12pentacene photophysical parameters including intersystem crossing . Apparently (and not surprisingly), the local pentacene environment this... pentacene molecules inp-terphenyl, both stable as well as spectrally diffusing single molecules can be observed. 20 DISTRIBUTION/AVAILABILITY OF ABSTRACT 121...with ultrathin sublimed crystals have removed this obstacle. For the case of pentacene impurities in crystals of p-terphenyl, we observe two radically

Influence of crystal structure on the Co{sup II} diffusion behavior in the Zn{sub 1-x}Co{sub x}O system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peiteado, M.; Makovec, D.; Villegas, M.

2008-09-15

The solid state interaction of the Zn{sub 1-x}Co{sub x}O nominal system is investigated by means of diffusion couples and analysis of co-precipitated samples. The formation of a homogeneous Co:ZnO solid solution is found to be determined by the crystal structure from which Co{sup II} ions diffuse into the wurtzite lattice. No diffusion is observed whenever the CoO rock-salt structure is formed from the Co{sup II} precursor. On the contrary, the diffusion from the Co{sub 3}O{sub 4} spinel phase is feasible but has a limited temperature range defined by the reduction at a high temperature of Co{sup III}-Co{sup II}, since thismore » process again leads to the formation of the rock-salt structure. However, when using a highly reactive and homogeneous co-precipitated starting powder, neither the spinel phase nor the rock-salt structure is formed, and a Co{sup II}:ZnO solid solution is obtained, which remains stable up to high temperatures. - Graphical abstract: Maximum diffusion distance for the ZnO-CoO{sub x} couple as a function of temperature. Dashed gray lines represent the temperature values at which the transformations between CoO and Co{sub 3}O{sub 4} compounds take place.« less

Rondorfite-type structure — XPS and UV–vis study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dulski, M., E-mail: mateusz.dulski@smcebi.edu.pl; A.Chelkowski Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007 Katowice; Bilewska, K., E-mail: kbilewska@us.edu.pl

2015-10-15

Highlights: • Structural and spectroscopic characterization of chlorosilicate mineral, rondorfite. • Characterization of main photoemission lines and valence band spectra. • The study of color origin’s using UV–vis spectroscopy. • Analysis of structural changes in context of origin of natural fluorescence. • Discussion of a new application possibilities of analyzed mineral - Abstract: This paper focuses on X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy of two different (green, orange) rondorfite samples. The differences in the sample color originate from various O/Cl ratios. The orange color was found to be related either to the isomorphic substitution of Fe{sup 3+}/Al{sup 3+} formore » Mg{sup 2+}, the presence of atypical [MgO{sub 4}] tetrahedrons in crystal structure or electronegativity of the sample. The tetrahedron is known to be very prone to accumulation of impurities and substitute atoms. Moreover, the XPS data showed tetrahedrally coordinated Mg{sup 2+} and isomorphic substitution of Al{sup 3+}/Fe{sup 3+} for Mg{sup 2+}, which influences local disordering and the point defects density and distribution. Non-equilibrium chlorine positions inside the crystal cages as well as Ca-Cl bonds have also been found. The XPS measurements as a function of temperature indicate occurrence of a structural transformation at about 770 K which is accompanied by a rotation of silicate tetrahedra within magnesiosilicate pentamer and luminescence disappearance.« less

Influence of Al substitution on magnetism and adsorption properties of hematite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Shanshan; Kang, Feifei; Yang, Xin

2015-08-15

A series of Al-substituted hematite was prepared. The structures and properties of as-prepared samples were characterized by various techniques. The magnetic property of the samples was determined and the adsorption of three dyes Acid Blue 74, Methylene Blue and Phenol Red onto the samples was investigated. The results showed that Al incorporation into the crystal structure of hematite occurs via isomorphous ionic substitution of Al for Fe. With increasing Al content, the particle size of samples decreases, the magnetization increases and the remanent magnetization remains unchanged. The coercivity of the samples increases with Al substitution up to n{sub Al}/n{sub Fe}more » 0.03, and then decreases as Al content further increases. Compared with Al-free hematite, Al-substituted samples exhibit better adsorption ability to all of the three dyes. The adsorption rates of the three dyes on the surface of Al substituted samples depend on the structure of dye, pH and Al content in hematite. - Graphical abstract: Effect of Al on the structure, magnetic properties and adsorption performance of hematite was investigated. - Highlights: • A series of Al-substituted α-Fe{sub 2}O{sub 3} was prepared. • Effect of Al content on the crystal structure and magnetic property of hematite was investigated. • Al-substituted hematite exhibits better adsorption ability than hematite.« less

New insights into the application of the valence rules in Zintl phases—Crystal and electronic structures of Ba{sub 7}Ga{sub 4}P{sub 9}, Ba{sub 7}Ga{sub 4}As{sub 9}, Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 6}CaAl{sub 4}Sb{sub 9}, and Ba{sub 6}CaGa{sub 4}Sb{sub 9}

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Hua; Stoyko, Stanislav; Bobev, Svilen, E-mail: bobev@udel.edu

Crystals of three new ternary pnictides—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9} have been prepared by reactions of the respective elements in molten Al or Pb fluxes. Single-crystal X-ray diffraction studies reveal that the three phases are isotypic, crystallizing in the orthorhombic Ba{sub 7}Ga{sub 4}Sb{sub 9}-type structure (space group Pmmn, Pearson symbol oP40, Z=2), for which only the prototype is known. The structure is based on TrPn{sub 4} tetrahedra (Tr=Al, Ga; Pn=P, As, Sb), connected in an intricate scheme into 1D-ribbons. Long interchain Pn–Pn bonds (d{sub P–P}>3.0 Å; d{sub As–As}>3.1 Å; d{sub Sb–Sb}>3.3 Å)more » account for the realization of 2D-layers, separated by Ba{sup 2+} cations. Applying the classic valance rules to rationalize the bonding apparently fails, and Ba{sub 7}Ga{sub 4}Sb{sub 9} has long been known as a metallic Zintl phase. Earlier theoretical calculations, both empirical and ab-initio, suggest that the possible metallic properties originate from filled anti-bonding Pn–Pn states, and the special roles of the “cations” in this crystal structure. To experimentally probe this hypothesis, we sought to synthesize the ordered quaternary phases Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga). Single-crystal X-ray diffraction work confirms Ba{sub 6.145(3)}Ca{sub 0.855}Al{sub 4}Sb{sub 9} and Ba{sub 6.235(3)}Ca{sub 0.765}Ga{sub 4}Sb{sub 9}, with Ca atoms preferably substituting Ba on one of the three available sites. The nuances of the five crystal structures are discussed, and the chemical bonding in Ba{sub 7}Ga{sub 4}As{sub 9} is interrogated by tight-binding linear muffin-tin orbital calculations. - Graphical abstract: The new Zintl phases—Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9}, and their quaternary variants Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga)—crystallize in the Ba{sub 7}Ga{sub 4}Sb{sub 9} structure type. The structures are based on TrPn{sub 4} tetrahedra (a perspective of the crystal structure is shown, as viewed along the c axis). - Highlights: • Ba{sub 7}Al{sub 4}Sb{sub 9}, Ba{sub 7}Ga{sub 4}P{sub 9}, and Ba{sub 7}Ga{sub 4}As{sub 9} are new compounds in the respective phase diagrams. • The quaternary phases Ba{sub 6}CaTr{sub 4}Sb{sub 9} (Tr=Al, Ga) show nearly ordered Ba/Ca distribution. • Very weak Pn–Pn bonds and pairing distortion are observed for Ba{sub 7}Ga{sub 4}Pn{sub 9} (Pn=P, As).« less

Second All-Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Abstracts of reports: Table of contents

NASA Astrophysics Data System (ADS)

Gershuni, G. Z.; Zhukhovitskiy, Y. M.

1984-01-01

s of reports are given which were presented at the Second All Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Topics inlcude: (1) features of crystallization of semiconductor materials under conditions of microacceleration; (2) experimental results of crystallization of solid solutions of CDTE-HGTE under conditions of weightlessness; (3) impurities in crystals cultivated under conditions of weightlessness; and (4) a numerical investigation of the distribution of impurities during guided crystallization of a melt.

Second All-Union Seminar on Hydromechanics and Heat and Mass Exchange in Weightlessness, summaries of reports

NASA Technical Reports Server (NTRS)

Gershuni, G. Z. (Editor); Zhukhovitskiy, Y. M. (Editor)

1984-01-01

Abstracts of reports are given which were presented at the Second All Union Seminar on Hydromechanics and Heat-Mass Transfer in Weightlessness. Topics include: (1) features of crystallization of semiconductor materials under conditions of microacceleration; (2) experimental results of crystallization of solid solutions of CDTE-HGTE under conditions of weightlessness; (3) impurities in crystals cultivated under conditions of weightlessness; and (4) a numerical investigation of the distribution of impurities during guided crystallization of a melt.

Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}: Structural, spectroscopic and computational studies on a sorosilicate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kahlenberg, Volker, E-mail: volker.kahlenberg@uibk.ac.at; Brunello, Emanuele; Hejny, Clivia

2015-05-15

Synthesis experiments in the system Li{sub 2}O–CaO–SiO{sub 2} resulted in the formation of single-crystals of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}. Structural investigations were based on single-crystal diffraction. At ambient conditions the compound has the following basic crystallographic data: hexagonal symmetry, space group P6{sub 1}22, a=5.0961(2) Å, c=41.264(2) Å, V=928.07(6) Å{sup 3}, Z=6. Structure solution was performed using direct methods. The final least-squares refinement calculations converged at a residual of R(|F|)=0.0260. From a structural point the lithium calcium silicate belongs to the group of pyrosilicates containing [Si{sub 2}O{sub 7}]-groups. Additional lithium and calcium cations are incorporated between the silicate dimers andmore » are coordinated by four and six nearest oxygen neighbours, respectively. Each [LiO{sub 4}]-tetrahedron shares two common corners with directly neighboring tetrahedra forming zweier single-chains which are running parallel to 〈1 0 0〉 in z-levels defined by the presence of the 6{sub 1}{sup [0} {sup 0} {sup 1]}-screw axes. From the corner-sharing [LiO{sub 4}]- and [SiO{sub 4}]-moieties a three dimensional framework can be constructed. An interesting feature of this framework is the presence of an O{sup [3]}-type bridging oxygen linking three tetrahedra (one [LiO{sub 4}]- and two [SiO{sub 4}]-units). Structural similarities with other silicates are discussed in detail. The high-temperature behavior of the Si–O, Ca–O and Li–O bond distances in Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} was investigated by in{sub -}situ single-crystal X-ray diffraction in the range between 65 and 700 °C. From the evolution of the lattice parameters, the thermal expansion tensor α{sub ij} has been determined. The structural characterization has been supplemented by micro-Raman spectroscopy. Interpretation of the spectroscopic data including the allocation of the bands to certain vibrational species has been aided by DFT-calculations. - Graphical abstract: Framework of [SiO{sub 4}]- and [LiO{sub 4}]-tetrahedra in the crystal structure of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7}. - Highlights: • We report the crystal structure of the sorosilicate Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} at ambient conditions. • The thermal expansion tensor as well as the evolution of the structure between 25 and 700 °C was studied. • A topological analysis of the tetrahedral framework based on [SiO{sub 4}]- and [LiO{sub 4}]-units is presented. • The crystal structure of Li{sub 2}Ca{sub 2}Si{sub 2}O{sub 7} is discussed with respect to related compounds. • Interpretation of the Raman spectra of the crystals has been aided by DFT-calculations.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Righettoni, Marco; Pratsinis, Sotiris E., E-mail: sotiris.pratsinis@ptl.mavt.ethz.ch

Highlights: • Flame-made WO{sub 3} nanoparticles with closely controlled crystal and grain size. • Dynamic phase transition of annealing of pure and Si-doped WO{sub 3} by in situ XRD. • Irreversible evolution of WO{sub 3} crystallinity by heating/cooling during its annealing. • Si-doping alters the WO{sub 3} crystallinity dynamics and stabilizes nanosized WO{sub 3}. • Flame-made nano-WO{sub 3} can sense NO at the ppb level. - Abstract: Tungsten trioxide is a semiconductor with distinct applications in gas sensors, catalysis, batteries and pigments. As such the transition between its different crystal structures during its annealing are of interest, especially for sensormore » applications. Here, WO{sub 3} nanoparticles with closely controlled crystal and grain size (9–15 nm) and phase composition are made by flame spray pyrolysis and the formation of different WO{sub 3} phases during annealing is investigated. Most notably, the dynamic phase transition and crystal size evolution of WO{sub 3} during heating and cooling is monitored by in situ X-ray diffraction revealing how metastable WO{sub 3} phases can be captured stably. The effect of Si-doping is studied since it is used in practise to control crystal growth and phase transition during metal oxide synthesis and processing. Finally the influence of annealing on the WO{sub 3} sensing performance of NO, a lung inflammation tracer in the human breath, is explored at the ppb-level.« less

Ag-ligand modified tungstovandates and their efficient catalysis degradation properties for methylene blue

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Ran; Zhang, Huixia; Liu, Yunping

Two polytungstovandates [Ag(mbpy){sub 2}][Ag{sub 2}(mbpy){sub 3}][VW{sub 5}O{sub 19}]·H{sub 2}O (1) and [Ag(mbpy)]{sub 2}[Ag(mbpy){sub 2}]{sub 4}[VW{sub 12}O{sub 40}] (2) (mbpy =4,4′-dimethyl-2,2′-bipyridyl), had been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. Single-crystal structural analysis revealed that the polyanionic clusters in two compounds are different: Lindqvist-type in 1 and α-Keggin-type in 2, respectively, while the cationic moieties in them are Ag-mbpy units. The experiments showed that this kind of hybrid crystal materials possesses more efficiently catalytic performance for the degradation of organic dye methylene blue (MB) in water solution under the UV irradiation. The significant degradation rate ofmore » MB can reach 89.9%, 94.9% by crystals 1 and 2 (40 mg) in the course of about 5 min. - Graphical abstract: Two Ag-ligand modified polytungstovandates had been synthesized and characterized, which were active in the catalytic degradation of organic dye methylene blue under the UV irradiation. - Highlights: • Two Ag-ligand modified tungstovandates were synthesized and characterized. • Weak interactions play important roles in constructing crystal frameworks. • Compounds are active to catalyze the degradation of methylene blue.« less

Electron density distribution and disordered crystal structure of 15R-SiAlON, SiAl{sub 4}O{sub 2}N{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Banno, Hiroki; Hanai, Takaaki; Asaka, Toru

2014-03-15

The crystal structure of SiAl{sub 4}O{sub 2}N{sub 4} was characterized by laboratory X-ray powder diffraction (CuKα{sub 1}). The title compound is trigonal with space group R3-bar m. The hexagonal unit-cell dimensions (Z=3) are a=0.301332(3) nm, c=4.18616(4) nm and V=0.3291825(5) nm{sup 3}. The initial structural model was successfully derived by the charge-flipping method and further refined by the Rietveld method. The final structural model showed the positional disordering of one of the three (Si,Al) sites. The maximum-entropy method-based pattern fitting (MPF) method was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensitymore » partitioning was minimized. The reliability indices calculated from the MPF were R{sub wp}=5.05%, S (=R{sub wp}/R{sub e})=1.21, R{sub p}=3.77%, R{sub B}=1.29% and R{sub F}=1.01%. The disordered crystal structure was successfully described by overlapping three types of domains with ordered atom arrangements. The distribution of atomic positions in one of the three types of domains can be achieved in the space group R3-bar m. The atom arrangements in the other two types of domains are noncentrosymmetrical with the space group R3m. These two structural configurations are related by the pseudo-symmetry inversion. -- Graphical abstract: A bird's eye view of electron densities up to 75.3% (0.133 nm{sup −3}) of the maximum on the plane parallel to (110) with the corresponding atomic arrangements of SiAl{sub 4}O{sub 2}N{sub 4}. Highlights: • Crystal structure of SiAl{sub 4}O{sub 2}N{sub 4} is determined by laboratory X-ray powder diffraction. • The atom arrangements are represented by the split-atom model. • The maximum-entropy method-based pattern fitting method is used to confirm the validity of the model. • The disordered structure is described by overlapping three types of domains with ordered atom arrangements.« less

MICROPATTERNED ORIENTED ZEOLITE MONOLAYER FILMS BY DIRECT IN-SITU CRYSTALLIZATION. (R828134)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Self-assembly of [UO{sub 2}X{sub 4}]{sup 2−} (X=Cl, Br) dianions with γ substituted pyridinium cations: Structural systematics and fluorescence properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Surbella, Robert G.; Andrews, Michael B.; Cahill, Christopher L., E-mail: cahill@gwu.edu

2016-04-15

Room temperature self-assembly of [UO{sub 2}X{sub 4}]{sup 2−} (X=Cl, Br) with γ substituted pyridinium cations has resulted in the formation of twelve compounds that were studied via single crystal X-ray diffraction and fluorescence spectroscopy. Systematic variation of electron donating groups on the pyridinium species is shown to influence the presence and/or strength of various supramolecular synthons, including hydrogen bonding and pi interactions. Combinations of such non-covalent interactions (NCIs) have given rise to a range of supramolecular assemblies, and are shown to influence uranyl emission by way of second sphere coordination to equatorial ligands. - Graphical abstract: Supramolecular assembly of themore » [UO{sub 2}Cl{sub 4}]{sup 2−} dianion with pyridinium cations is a viable synthetic route to the growth of uranyl containing single crystals.« less

Crystal structure of bacterial cell-surface alginate-binding protein with an M75 peptidase motif

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maruyama, Yukie; Ochiai, Akihito; Mikami, Bunzo

Research highlights: {yields} Bacterial alginate-binding Algp7 is similar to component EfeO of Fe{sup 2+} transporter. {yields} We determined the crystal structure of Algp7 with a metal-binding motif. {yields} Algp7 consists of two helical bundles formed through duplication of a single bundle. {yields} A deep cleft involved in alginate binding locates around the metal-binding site. {yields} Algp7 may function as a Fe{sup 2+}-chelated alginate-binding protein. -- Abstract: A gram-negative Sphingomonas sp. A1 directly incorporates alginate polysaccharide into the cytoplasm via the cell-surface pit and ABC transporter. A cell-surface alginate-binding protein, Algp7, functions as a concentrator of the polysaccharide in the pit.more » Based on the primary structure and genetic organization in the bacterial genome, Algp7 was found to be homologous to an M75 peptidase motif-containing EfeO, a component of a ferrous ion transporter. Despite the presence of an M75 peptidase motif with high similarity, the Algp7 protein purified from recombinant Escherichia coli cells was inert on insulin B chain and N-benzoyl-Phe-Val-Arg-p-nitroanilide, both of which are substrates for a typical M75 peptidase, imelysin, from Pseudomonas aeruginosa. The X-ray crystallographic structure of Algp7 was determined at 2.10 A resolution by single-wavelength anomalous diffraction. Although a metal-binding motif, HxxE, conserved in zinc ion-dependent M75 peptidases is also found in Algp7, the crystal structure of Algp7 contains no metal even at the motif. The protein consists of two structurally similar up-and-down helical bundles as the basic scaffold. A deep cleft between the bundles is sufficiently large to accommodate macromolecules such as alginate polysaccharide. This is the first structural report on a bacterial cell-surface alginate-binding protein with an M75 peptidase motif.« less

Crystal Structure of the Marburg Virus VP35 Oligomerization Domain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruhn, Jessica F.; Kirchdoerfer, Robert N.; Urata, Sarah M.

ABSTRACT Marburg virus (MARV) is a highly pathogenic filovirus that is classified in a genus distinct from that of Ebola virus (EBOV) (generaMarburgvirusandEbolavirus, respectively). Both viruses produce a multifunctional protein termed VP35, which acts as a polymerase cofactor, a viral protein chaperone, and an antagonist of the innate immune response. VP35 contains a central oligomerization domain with a predicted coiled-coil motif. This domain has been shown to be essential for RNA polymerase function. Here we present crystal structures of the MARV VP35 oligomerization domain. These structures and accompanying biophysical characterization suggest that MARV VP35 is a trimer. In contrast, EBOVmore » VP35 is likely a tetramer in solution. Differences in the oligomeric state of this protein may explain mechanistic differences in replication and immune evasion observed for MARV and EBOV. IMPORTANCEMarburg virus can cause severe disease, with up to 90% human lethality. Its genome is concise, only producing seven proteins. One of the proteins, VP35, is essential for replication of the viral genome and for evasion of host immune responses. VP35 oligomerizes (self-assembles) in order to function, yet the structure by which it assembles has not been visualized. Here we present two crystal structures of this oligomerization domain. In both structures, three copies of VP35 twist about each other to form a coiled coil. This trimeric assembly is in contrast to tetrameric predictions for VP35 of Ebola virus and to known structures of homologous proteins in the measles, mumps, and Nipah viruses. Distinct oligomeric states of the Marburg and Ebola virus VP35 proteins may explain differences between them in polymerase function and immune evasion. These findings may provide a more accurate understanding of the mechanisms governing VP35's functions and inform the design of therapeutics.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chao, Tzu-Ling; Yang, Chen-I., E-mail: ciyang@thu.edu.tw

The preparations and properties of three new homochiral three-dimensional (3D) coordination polymers, [M(D-cam)(pyz)(H{sub 2}O){sub 2}]{sub n} (M=Co (1) and Ni (2); D-H{sub 2}cam=(+) D-camphoric acid; pyz=pyrazine) and [Mn{sub 2}(D-cam){sub 2}(H{sub 2}O){sub 2}] (3), under solvothermal conditions is described. Single-crystal X-ray diffraction analyses revealed that all of compounds are homochiral 3D structure. 1 and 2 are isostructural and crystallize in the trigonal space group P3{sub 2}21, while 3 crystallizes in monoclinic space group P2{sub 1}. The structure of 1 and 2 consists of metal-D-cam helical chains which are pillared with pyrazine ligands into a 3D framework structure and 3 features amore » 3D homochiral framework involving one-dimensional manganese-carboxylate chains that are aligned parallel to the b axis. Magnetic susceptibility data of all compounds were collected. The findings indicate that μ{sub 2}-pyrazine dominate weak antiferromagnetic coupling within 1 and 2, while 3 exhibits antiferromagnetic behavior through the carboxylate groups of D-cam ligand. -- Graphical abstract: The preparations and properties of three new homochiral three-dimensional (3D) coordination polymers, [M(D-cam)(pyz)(H{sub 2}O){sub 2}]{sub n} (M=Co (1) and Ni (2); D-H{sub 2}cam=(+) D-camphoric acid; pyz=pyrazine) and [Mn{sub 2}(D-cam){sub 2}(H{sub 2}O){sub 2}] (3), under solvothermal conditions is described. Single-crystal X-ray diffraction analyses revealed that all of compounds are homochiral 3D structure. 1 and 2 are isostructural and crystallize in the trigonal space group P3{sub 2}21, while 3 crystallizes in monoclinic space group P2{sub 1}. The structure of 1 and 2 consists of metal-D-cam helical chains which are pillared with pyrazine ligands into a 3D framework structure and 3 features a 3D homochiral framework involving one-dimensional manganese-carboxylate chains that are aligned parallel to the b axis. Magnetic susceptibility data of all compounds were collected. The findings indicate that μ{sub 2}-pyrazine dominate weak antiferromagnetic coupling within 1 and 2, while 3 exhibits antiferromagnetic behavior through the carboxylate groups of D-cam ligand. Highlights: • Three homochiral 3D coordination polymers were synthesized. • 1 and 2 are 3D structure with metal-D-cam helical chains pillared by pyrazine. • 3 shows a 3D homochiral framework involving 1D manganese-carboxylate chains. • Magnetic data analysis indicates that 1–3 exhibit weak antiferromagnetic coupling.« less

Mild hydrothermal crystal growth of new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}: Structures, optical and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeon, Jeongho; Smith, Mark D.; Tapp, Joshua

Two new uranium(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} (1) and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} (2), were synthesized through an in situ mild hydrothermal route, and were structurally characterized by single crystal X-ray diffraction. The compounds exhibit complex crystal structures composed of corner- or edge-shared UF{sub 9} and MF{sub 6} (M=Mg, Mn) polyhedra, forming hexagonal channels in the three-dimensional framework, in which ordered or disordered divalent metal and sodium atoms reside. The large hexagonal voids contain the nearly regular M(II)F{sub 6} octahedra and sodium ions, whereas the small hexagonal cavities include M(II) and sodium ions on a mixed-occupied site.more » Magnetic susceptibility measurements yielded effective magnetic moments of 8.36 and 11.6 µ{sub B} for 1 and 2, respectively, confirming the presence and oxidation states of U(IV) and Mn(II). The large negative Weiss constants indicate the spin gap between a triplet and a singlet state in the U(IV). Magnetization data as a function of applied fields revealed that 2 exhibits paramagnetic behavior due to the nonmagnetic singlet ground state of U(IV) at low temperature. UV–vis diffuse reflectance and X-ray photoelectron spectroscopy data were also analyzed. - Graphical abstract: Two new quaternary U(IV) fluorides, Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30}, were crystallized via an in situ reduction step of U(VI) to U(IV) under mild hydrothermal conditions. The compounds show complex crystal structures based on the 3-D building block of U{sub 6}F{sub 30}. Magnetic property measurements revealed that the U(IV) exhibits a nonmagnetic singlet ground state at low temperature with a spin gap. - Highlights: • Na{sub 3.13}Mg{sub 1.43}U{sub 6}F{sub 30} and Na{sub 2.50}Mn{sub 1.75}U{sub 6}F{sub 30} have been synthesized and characterized. • The U(IV) fluorides exhibit complex three-dimensional crystal structures. • The optical properties were investigated. • Magnetic susceptibility data were collected.« less

Oxygen transport as a structure probe for heterogeneous polymeric systems

NASA Astrophysics Data System (ADS)

Hu, Yushan

Although permeability of small molecules is often measured as an important performance property, deeper analysis of the transport characteristics provides insight into polymer structure, especially if used in combination with other characterization techniques. Transport of small gas molecules senses the permeable amorphous structure and probes the nature of free volume. This work focuses on oxygen transport, supplemented with other methods of physical analysis, as a probe for: (1) the nature of free volume and crystalline morphology in the crystallized glassy state, (2) the nature of free volume and hierarchical structure in liquid crystalline polymers, and (3) the role of dispersed polyamide phase geometry on oxygen barrier properties of poly(ethylene terephthalate) (PET)/polyamide blends. In the first part, the improvement in oxygen-barrier properties of glassy polyesters by crystallization was examined. Examples included poly(ethylene naphthalate) (PEN), and a copolymer based on PET in which 55 mol% terephthalate was replaced with 4,4'-bibenzoate. Explanation of the unexpectedly high solubility of crystallized PEN required a two-phase transport model consisting of an impermeable crystalline phase of constant density and a permeable amorphous phase of variable density. The resulting relationship between oxygen solubility and amorphous phase density was consistent with free volume concepts of gas sorption. In the second part, oxygen barrier properties of liquid crystalline (LC) polyesters based on poly(diethylene glycol 4,4'-bibenzoate) (PDEGBB) were studied. This study extended the 2-phase transport model for oxygen transport of non-LC crystalline polymers to a smectic LCP. It was possible to systematically vary the solid state structure of (PDEGBB) from LC glass to crystallized LC glass. The results were consistent with a liquid crystalline state intermediate between the permeable amorphous glass and the impermeable 3-dimensional crystal. In this interpretation, LC order naturally led to inherently low gas solubility. In the third part, improvement of gas-barrier properties of poly(ethylene terephthalate) (PET) by blending with an aromatic polyamide, either poly(m-xylylene adipamide) (MXD6) or a copolyamide based on MXD6 in which 12 mol% adipamide was replaced with isophthalamide (MXD6-12I), was studied. Aromatic polyamides provided higher barrier than aliphatic polyamides, and unlike aliphatic polyamides, the aromatic polyamides retained high barrier under conditions of high humidity, making them more suitable for beverage packaging applications. (Abstract shortened by UMI.)

Synthesis, structures and properties of the new lithium cobalt(II) phosphate Li{sub 4}Co(PO{sub 4}){sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glaum, R., E-mail: rglaum@uni-bonn.de; Gerber, K.; Schulz-Dobrick, M.

2012-04-15

{alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} has been synthesized and crystallized by solid-state reactions. The new phosphate crystallizes in the monoclinic system (P2{sub 1}/a, Z=4, a=8.117(3) Angstrom-Sign , b=10.303(8) Angstrom-Sign , c=8.118(8) Angstrom-Sign , {beta}=104.36(8) Angstrom-Sign ) and is isotypic to {alpha}-Li{sub 4}Zn(PO{sub 4}){sub 2}. The structure of {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} has been determined from single-crystal X-ray diffraction data {l_brace}R{sub 1}=0.040, wR{sub 2}=0.135, 2278 unique reflections with F{sub o}>4{sigma}(F{sub o}){r_brace}. The crystal structure, which might be regarded as a superstructure of the wurtzite structure type, is build of layers of regular CoO{sub 4}, PO{sub 4} and Li1O{sub 4} tetrahedra. Lithium atomsmore » Li2, Li3 and Li4 are located between these layers. Thermal investigations by in-situ XRPD, DTA/TG and quenching experiments suggest decomposition followed by formation and phase transformation of Li{sub 4}Co(PO{sub 4}){sub 2}: {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} Long-Rightwards-Double-Arrow {sup 442 Degree-Sign C}{beta}-Li{sub 3}PO{sub 4}+LiCoPO{sub 4} Rightwards-Harpoon-Over-Leftwards-Harpoon {sup 773 Degree-Sign C}{beta}-Li{sub 4}Co(PO{sub 4}){sub 2} Long-Rightwards-Double-Arrow {sup quenchingto25 Degree-Sign C}{alpha}-Li{sub 4} Co(PO{sub 4}){sub 2} According to HT-XRPD at {theta}=850 Degree-Sign C{beta}-Li{sub 4}Co(PO{sub 4}){sub 2} (Pnma, Z=2, 10.3341(8) A, b=6.5829(5) A, c=5.0428(3) Angstrom-Sign ) is isostructural to {gamma}-Li{sub 3}PO{sub 4}. The powder reflectance spectrum of {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2} shows the typical absorption bands for the tetrahedral chromophore [Co{sup II}O{sub 4}]. - Graphical abstract: The complex formation and decomposition behavior of Li{sub 4}Co(PO{sub 4}){sub 2} with temperature has been elucidated. The crystal structure of its {alpha}-phase was determined from single crystal data, HT-XRPD allowed derivation of a structure model for the {beta}-phase. Both modifications belong to the Li{sub 3}PO{sub 4} structure family. Highlights: Black-Right-Pointing-Pointer Li{sub 4}Co(PO{sub 4}){sub 2} exhibits complex thermal behavior. Black-Right-Pointing-Pointer The new phosphate belongs to the Li{sub 3}PO{sub 4} structure family. Black-Right-Pointing-Pointer A single-crystal structure analysis is provided for the metastable {alpha}-Li{sub 4}Co(PO{sub 4}){sub 2}. Black-Right-Pointing-Pointer From HT-XRPD data a cation distribution model is developed for {beta}-Li{sub 4}Co(PO{sub 4}){sub 2}. Black-Right-Pointing-Pointer No electrochemical delithiation is observed up to 5 V.« less

Structural properties of ultrafine Ba-hexaferrite nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Makovec, Darko, E-mail: Darko.Makovec@ijs.si; Primc, Darinka; Sturm, Saso

2012-12-15

Crystal structure of ultrafine Ba-hexaferrite (BaFe{sub 12}O{sub 19}) nanoparticles was studied using X-ray diffractometry (XRD), high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDXS), X-ray absorption fine structure (XAFS), and Moessbauer spectroscopy (MS), to be compared to the structure of larger nanoparticles and the bulk. The nanoparticles were synthesized with hydrothermal treatment of an appropriate suspension of Ba and Fe hydroxides in the presence of a large excess of OH{sup -}. The ultrafine nanoparticles were formed in a discoid shape, {approx}10 nm wide and only {approx}3 nm thick, comparable to the size of the hexagonal unit cell in the c-direction.more » The HRTEM image analysis confirmed the hexaferrite structure, whereas EDXS showed the composition matching the BaFe{sub 12}O{sub 19} formula. XAFS and MS analyses showed considerable disorder of the structure, most probably responsible for the low magnetization. - Graphical abstract: Left: HREM image of an ultrafine Ba-hexaferrite nanoparticle (inset: TEM image of the nanoparticles); Right: the experimental HRTEM image is compared with calculated image and corresponding atomic model. Highlights: Black-Right-Pointing-Pointer Crystal structure of ultrafine Ba-hexaferrite (BaFe{sub 12}O{sub 19}) nanoparticles was compared to the structure of the bulk. Black-Right-Pointing-Pointer Thickness the discoid nanoparticles was comparable to the size of the hexagonal unit cell in the c-direction. Black-Right-Pointing-Pointer Considerable disorder of the nanoparticles' structure is most probably responsible for their low magnetization.« less

2D and 3D photonic crystal materials for photocatalysis and electrochemical energy storage and conversion

PubMed Central

Collins, Gillian; Armstrong, Eileen; McNulty, David; O’Hanlon, Sally; Geaney, Hugh; O’Dwyer, Colm

2016-01-01

Abstract This perspective reviews recent advances in inverse opal structures, how they have been developed, studied and applied as catalysts, catalyst support materials, as electrode materials for batteries, water splitting applications, solar-to-fuel conversion and electrochromics, and finally as photonic photocatalysts and photoelectrocatalysts. Throughout, we detail some of the salient optical characteristics that underpin recent results and form the basis for light-matter interactions that span electrochemical energy conversion systems as well as photocatalytic systems. Strategies for using 2D as well as 3D structures, ordered macroporous materials such as inverse opals are summarized and recent work on plasmonic–photonic coupling in metal nanoparticle-infiltrated wide band gap inverse opals for enhanced photoelectrochemistry are provided. PMID:27877904

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumada, Nobuhiro, E-mail: kumada@yamanashi.ac.jp; Nakamura, Ayumi; Miura, Akira

A new lithium copper bismuth oxide, LiCuBiO{sub 4} was prepared by hydrothermal reaction using NaBiO{sub 3}0.1*4H{sub 2}O. The crystal structural model of this compound was refined by using synchrotron X-ray powder diffraction data. This bismuthate has the LiCuSbO{sub 4} related structure with the orthorhombic cell (Space group: Pnma) of a=10.9096(9), b=5.8113(5) and c=5.0073(4) Å, and the final R-factors were R{sub wp}=4.84 and R{sub p}=3.58%. This compound is the first example of a lithium copper bismuthate containing Bi{sup 5+}. An antiferromagnetic ordering of Cu{sup 2+} moment was observed at 6 K. - Graphical abstract: In the crystal structure of LiCuBiO{sub 4}more » all metal atoms are coordinated octahedrally by six O atoms and LiO{sub 6} and CuO{sub 6} octahedra form the one-dimensional chains by edge-sharing along the b-axis. The LiO{sub 6} and CuO{sub 6} chains form the layer by face-sharing in the bc plane. The Bi atoms are placed in that interlayer and BiO{sub 6} octahedra are edge-sharing with LiO{sub 6} and CuO{sub 6} octahedra. - Highlights: • A new lithium copper bismuth oxide, LiCuBiO{sub 4} is prepared by hydrothermal reaction. • The crystal structure of LiCuBiO{sub 4} is closely related with that of LiCuSbO{sub 4}. • This new compound exhibits an antiferromagnetic ordering of Cu{sup 2+} moment at 6 K.« less

Pyrite footprinting of RNA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schlatterer, Joerg C., E-mail: joerg.schlatterer@einstein.yu.edu; Wieder, Matthew S.; Jones, Christopher D.

2012-08-24

Highlights: Black-Right-Pointing-Pointer RNA structure is mapped by pyrite mediated {sup {center_dot}}OH footprinting. Black-Right-Pointing-Pointer Repetitive experiments can be done in a powdered pyrite filled cartridge. Black-Right-Pointing-Pointer High {sup {center_dot}}OH reactivity of nucleotides imply dynamic role in Diels-Alderase catalysis. -- Abstract: In RNA, function follows form. Mapping the surface of RNA molecules with chemical and enzymatic probes has revealed invaluable information about structure and folding. Hydroxyl radicals ({sup {center_dot}}OH) map the surface of nucleic acids by cutting the backbone where it is accessible to solvent. Recent studies showed that a microfluidic chip containing pyrite (FeS{sub 2}) can produce sufficient {sup {center_dot}}OH tomore » footprint DNA. The 49-nt Diels-Alder RNA enzyme catalyzes the C-C bond formation between a diene and a dienophile. A crystal structure, molecular dynamics simulation and atomic mutagenesis studies suggest that nucleotides of an asymmetric bulge participate in the dynamic architecture of the ribozyme's active center. Of note is that residue U42 directly interacts with the product in the crystallized RNA/product complex. Here, we use powdered pyrite held in a commercially available cartridge to footprint the Diels-Alderase ribozyme with single nucleotide resolution. Residues C39 to U42 are more reactive to {sup {center_dot}}OH than predicted by the solvent accessibility calculated from the crystal structure suggesting that this loop is dynamic in solution. The loop's flexibility may contribute to substrate recruitment and product release. Our implementation of pyrite-mediated {sup {center_dot}}OH footprinting is a readily accessible approach to gleaning information about the architecture of small RNA molecules.« less

Structure and magnetic properties of RE{sub 2}CuIn{sub 3} (RE=Ce, Pr, Nd, Sm and Gd)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tyvanchuk, Yuriy B.; Szytula, Andrzej; Zarzycki, Arkadiusz

2008-12-15

The ternary copper indides RE{sub 2}CuIn{sub 3}{identical_to}RECu{sub 0.5}In{sub 1.5} (RE=Ce, Pr, Nd, Sm and Gd) were synthesized from the elements in sealed tantalum tubes in an induction furnace. They crystallize with the CaIn{sub 2}-type structure, space group P6{sub 3}/mmc, with a statistical occupancy of copper and indium on the tetrahedral substructure. These indides show homogeneity ranges RECu{sub x}In{sub 2-x}. Single crystal structure refinements were performed for five crystals: CeCu{sub 0.66}In{sub 1.34} (a=479.90(7) pm, c=768.12(15) pm), PrCu{sub 0.52}In{sub 1.48} (a=480.23(7) pm, c=759.23(15) pm), NdCu{sub 0.53}In{sub 1.47} (a=477.51(7) pm, c=756.37(15) pm), SmCu{sub 0.46}In{sub 1.54} (a=475.31(7) pm, c=744.77(15) pm), and GdCu{sub 0.33}In{sub 1.67}more » (a=474.19(7), c=737.67(15) pm). Temperature-dependent susceptibility measurements show antiferromagnetic ordering at T{sub N}=4.7 K for Pr{sub 2}CuIn{sub 3} and Nd{sub 2}CuIn{sub 3} and 15 K for Sm{sub 2}CuIn{sub 3}. Fitting of the susceptibility data of the samarium compound revealed an energy gap {delta}E=39.7(7) K between the ground and the first excited levels. - Graphical abstract: The CaIn{sub 2}-type structure of Sm{sub 2}CuIn{sub 3}.« less

Crystal structure and X-ray photoemission spectroscopic study of A{sub 2}LaMO{sub 6} [A=Ba, Ca; M=Nb, Ta

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Alo, E-mail: alo_dutta@yahoo.com; Saha, Sujoy; Kumari, Premlata

2015-09-15

The X-ray photoemission spectroscopic (XPS) study of the double perovskite oxides A{sub 2}LaMO{sub 6} [A=Ba, Ca; M=Nb, Ta] synthesized by the solid-state reaction technique has been carried out to investigate the nature of the chemical state of the constituent ions and the bonding between them. The Rietveld refinement of the X-ray diffraction patterns suggests the monoclinic crystal structure of all the materials at room temperature. The negative and positive chemical shifts of the core level XPS spectrum of O-1s and Nb-3d{sub 3/2}/Ta-4f{sub 5/2} respectively suggest the covalent bonding between Nb/Ta cations and O ion. The change of the bonding strengthmore » between the anion and the cations from one material to another has been analyzed. The vibrational property of the materials is investigated using the room temperature Raman spectra. A large covalency of Ta-based compound than Nb compound is confirmed from the relative shifting of the Raman modes of the materials. - Graphical abstract: Crystal structure of two perovskite oxides CLN and CLT is investigated. XPS study confirms the two different co-ordination environments of Ca and covalent bonding between B-site cations and O-ion. - Highlights: • Ordered perovskite structure obtained by Rietveld refinement of XRD patterns. • Study of nature of chemical bonding by X-ray photoemission spectroscopy. • Opposite chemical shift of d-states of Nb/Ta with respect to O. • Covalent bonding between d-states of Nb/Ta and O. • Relative Raman shifts of CLN and CLT substantiate the more covalent character of Ta than Nb.« less

Purification and characterization pecan (Carya Illinoinensis) vicilin, a putative food allergen (abstract)

USDA-ARS?s Scientific Manuscript database

The pecan seed storage protein vicilin, a putative food allergen, was recombinantly expressed for and purified by a combination of metal affinity and gel filtration chromatography. The protein was crystallized and studied by crystallography. The obtained crystals belonged to space group P212121 with...

Easy To Synthesize, Robust Organo‐osmium Asymmetric Transfer Hydrogenation Catalysts

PubMed Central

Coverdale, James P. C.; Sanchez‐Cano, Carlos; Clarkson, Guy J.; Soni, Rina

2015-01-01

Abstract Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori‐type RuII catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X‐ray crystal structures of the 16‐electron OsII catalysts are almost identical to those of RuII. Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The OsII catalysts are readily synthesised (within 1 h) and exhibit excellent enantioselectivity in ATH reactions of ketones. PMID:25853228

International Conference on Liquid and Amorphous Metals (5th) Held at Los Angeles, California on August 15-19, 1983. Abstract.

DTIC Science & Technology

1983-08-19

Wang : CORROSION RESISTANCE OF AMORPHOUS AND CRYSTALLIZED Fe-Ni-Cr-W ALLOYS " 12:25 am M4 A. Yokoyama, H. Komiyama, H. Inoue, T. Masunoto, and H.M. Kimura...ENTHALPY RELAXATION IN PdNi ALLOY GLASSES 2:30 pm N3 A.I. Taub and J.L. Walter: SCALING THE COMPOSITION DEPENDENCE OF ATOMIC TRANSPORT AND STRUCTURAL...Cnn, L.Q. Wang , Y. Obi, and K. Fukamichi: LOW- TEMPERATURE SPECIFIC HEAT OF Fe-Zr AND Ni-Zr AMORPHOUS ALLOYS 2:15 pm 02 S.J. Poon: FLUX FLOW RESISTIVITY

Synthesis and characterization of hollow mesoporous BaFe{sub 12}O{sub 19} spheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Xia; Department of Chemical and Biological Engineering, The University of Alabama, Tuscaloosa, AL 35487; Park, Jihoon

2015-02-15

A facile method is reported to synthesize hollow mesoporous BaFe{sub 12}O{sub 19} spheres using a template-free chemical etching process. Hollow BaFe{sub 12}O{sub 19} spheres were synthesized by conventional spray pyrolysis. The mesoporous structure is achieved by alkaline ethylene glycol etching at 185 °C, with the porosity controlled by the heating time. The hollow porous structure is confirmed by SEM, TEM, and FIB-FESEM characterization. The crystal structure and magnetic properties are not significantly affected after the chemical etching process. The formation mechanism of the porous structure is explained by grain boundary etching. - Graphical abstract: Hollow spherical BaFe{sub 12}O{sub 19} particlesmore » are polycrystalline with both grains and grain boundaries. Grain boundaries have less ordered structure and lower stability. When the particles are exposed to high temperature alkaline ethylene glycol, the grain boundaries are etched, leaving small grooves between grains. These grooves allow ethylene glycol to diffuse inside to further etch the grains. As the grain size decreases, gaps appear on the particle surfaces, and a porous structure is finally formed. - Highlights: • Two-step synthesis method for hollow mesoporous BaFe{sub 12}O{sub 19} spheres is proposed. • Porosity of the product can be regulated by controlling the second step of chemical etching. • The crystal structure and magnetic properties are examined to be little affected during the chemical etching. • The mesoporous structure formation mechanism is explained by grain boundary etching.« less

Iridescent cellulose nanocrystal films: the link between structural colour and Bragg’s law

NASA Astrophysics Data System (ADS)

Nguyen, Thanh-Dinh; Sierra, Egoitz; Eguiraun, Harkaitz; Lizundia, Erlantz

2018-07-01

Structural colour is a phenomenon found in nature, which provides plants and animals with vibrant optical properties. The production of this colour is based on the interaction of incident light with the hierarchical organisation of submicron- and micron-sized layered structures. Cellulose nanocrystals (CNCs) are anisotropic building units formed by acid hydrolysis of native cellulose microfibers, which can disperse in aqueous media to form a photonic liquid crystal. One fascinating example of the appearance of biomimetic colour is the supramolecular assembly of CNCs into iridescent layered structures that rotate along a helical screw to yield a long-range chiral nematic order. A quick, simple and engaging experiment that allows the establishment of a direct relation between the structural colour and underlying mechanism of the light interaction with these hierarchically structured materials is reported. The obtained colour changes are explained within the theoretical framework provided by Bragg’s law and may provide an easy way to observe the macroscopic manifestation of this often abstract concept.

Magnetic and charge transport properties of the Na-based Os oxide pyrochlore

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Y.G., E-mail: SHI.Youguo@nims.go.j; International Center for Materials Nanoarchitectonics; JST, Transformative Research-Project on Iron Pnictides

2009-04-15

The Na-based osmium oxide pyrochlore was synthesized for the first time by an ion-exchange method using KOs{sub 2}O{sub 6} as a host. The composition was identified as Na{sub 1.4}Os{sub 2}O{sub 6}.H{sub 2}O by electron probe micro-analysis, thermogravimetric analysis, and structural analysis using synchrotron X-ray diffraction. Na{sub 1.4}Os{sub 2}O{sub 6}.H{sub 2}O crystallizes in a regular pyrochlore structure with some defects (space group: Fd-3m, a=10.16851(1) A). Electrical resistivity, heat capacity, and magnetization measurements clearly showed absence of superconductivity down to 2 K, being in large contrast to what was found for the beta-type pyrochlore superconductor AOs{sub 2}O{sub 6} (A=Cs, Rb, and K).more » The Sommerfeld coefficient is 22 mJ K{sup -2} mol{sup -1}, being the smallest among AOs{sub 2}O{sub 6}. A magnetic anomaly at {approx}57 K and associated magneto-resistance (+3.7% at 2 K in 70 kOe) were found. - Graphical abstract: Crystal structure of the Na-based Os oxide pyrochlore Na{sub 1.4}Os{sub 2}O{sub 6}.H{sub 2}O.« less

Characterization of Heavy Oxide Inorganic Scintillator Crystals for Direct Detection of Fast Neutrons Based on Inelastic Scattering

DTIC Science & Technology

2015-03-01

HEAVY OXIDE INORGANIC SCINTILLATOR CRYSTALS FOR DIRECT DETECTION OF FAST NEUTRONS BASED ON INELASTIC SCATTERING by Philip R. Rusiecki...HEAVY OXIDE INORGANIC SCINTILLATOR CRYSTALS FOR DIRECT DETECTION OF FAST NEUTRONS BASED ON INELASTIC SCATTERING 6. AUTHOR(S) Philip R. Rusiecki 7...ABSTRACT (maximum 200 words) Heavy oxide inorganic scintillators may prove viable in the detection of fast neutrons based on the mechanism of

Crystal structure of Helicobacter pylori neutrophil-activating protein with a di-nuclear ferroxidase center in a zinc or cadmium-bound form

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yokoyama, Hideshi, E-mail: h-yokoya@u-shizuoka-ken.ac.jp; Tsuruta, Osamu; Akao, Naoya

2012-06-15

Highlights: Black-Right-Pointing-Pointer Structures of a metal-bound Helicobacter pylori neutrophil-activating protein were determined. Black-Right-Pointing-Pointer Two zinc ions were tetrahedrally coordinated by ferroxidase center (FOC) residues. Black-Right-Pointing-Pointer Two cadmium ions were coordinated in a trigonal-bipyramidal and octahedral manner. Black-Right-Pointing-Pointer The second metal ion was more weakly coordinated than the first at the FOC. Black-Right-Pointing-Pointer A zinc ion was found in one negatively-charged pore suitable as an ion path. -- Abstract: Helicobacter pylori neutrophil-activating protein (HP-NAP) is a Dps-like iron storage protein forming a dodecameric shell, and promotes adhesion of neutrophils to endothelial cells. The crystal structure of HP-NAP in a Zn{sup 2+}-more » or Cd{sup 2+}-bound form reveals the binding of two zinc or two cadmium ions and their bridged water molecule at the ferroxidase center (FOC). The two zinc ions are coordinated in a tetrahedral manner to the conserved residues among HP-NAP and Dps proteins. The two cadmium ions are coordinated in a trigonal-bipyramidal and distorted octahedral manner. In both structures, the second ion is more weakly coordinated than the first. Another zinc ion is found inside of the negatively-charged threefold-related pore, which is suitable for metal ions to pass through.« less

Syntheses, structure and magnetic properties of two vanadate garnets Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Nannan; College of Materials Science and Engineering, Fuzhou University, Fuzhou, Fujian 350108; He, Zhangzhen, E-mail: hcz1988@hotmail.com

2015-08-15

Two vanadate compounds Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) have been synthesized by a high-temperature solid-state reaction. The compounds are found to crystallize in the cubic system with a space group Ia-3d, which exhibit a typical garnet structural framework. Magnetic measurements show that Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) exhibit similar magnetic behaviors, in which Ca{sub 5}Co{sub 4}V{sub 6}O{sub 24} possesses an antiferromagnetic ordering at T{sub N}=~6 K while Ca{sub 5}Ni{sub 4}V{sub 6}O{sub 24} shows an antiferromagnetic ordering at T{sub N}=~7 K. - Graphical abstract: Garnet vanadate compounds Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) have been synthesizedmore » by a high-temperature solid-state reaction. Structural features and magnetic behaviors are also investigated. - Highlights: • New type of garnet vanadates Ca{sub 5}M{sub 4}V{sub 6}O{sub 24} (M=Co, Ni) are synthesized by a high-temperature solid-state reaction. • Structural features are confirmed by single crystal samples. • Magnetic behaviors are firstly investigated in the systems.« less

Crystal Structure of the Heme d1 Biosynthesis Enzyme NirE in Complex with Its Substrate Reveals New Insights into the Catalytic Mechanism of S-Adenosyl-l-methionine-dependent Uroporphyrinogen III Methyltransferases*

PubMed Central

Storbeck, Sonja; Saha, Sayantan; Krausze, Joern; Klink, Björn U.; Heinz, Dirk W.; Layer, Gunhild

2011-01-01

During the biosynthesis of heme d1, the essential cofactor of cytochrome cd1 nitrite reductase, the NirE protein catalyzes the methylation of uroporphyrinogen III to precorrin-2 using S-adenosyl-l-methionine (SAM) as the methyl group donor. The crystal structure of Pseudomonas aeruginosa NirE in complex with its substrate uroporphyrinogen III and the reaction by-product S-adenosyl-l-homocysteine (SAH) was solved to 2.0 Å resolution. This represents the first enzyme-substrate complex structure for a SAM-dependent uroporphyrinogen III methyltransferase. The large substrate binds on top of the SAH in a “puckered” conformation in which the two pyrrole rings facing each other point into the same direction either upward or downward. Three arginine residues, a histidine, and a methionine are involved in the coordination of uroporphyrinogen III. Through site-directed mutagenesis of the nirE gene and biochemical characterization of the corresponding NirE variants the amino acid residues Arg-111, Glu-114, and Arg-149 were identified to be involved in NirE catalysis. Based on our structural and biochemical findings, we propose a potential catalytic mechanism for NirE in which the methyl transfer reaction is initiated by an arginine catalyzed proton abstraction from the C-20 position of the substrate. PMID:21632530

Phase equilibria in the NaF-CdO-NaPO{sub 3} system at 873 K and crystal structure and physico-chemical characterizations of the new Na{sub 2}CdPO{sub 4}F fluorophosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aboussatar, Mohamed; Laboratoire de Physico-Chimie de l’État Solide, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3000 Sfax; Mbarek, Aïcha

Isothermal sections of the diagram representing phase relationships in the NaF-CdO-NaPO{sub 3} system have been investigated by solid state reactions and powder X-ray diffraction. This phase diagram investigation confirms the polymorphism of the NaCdPO{sub 4} side component and the structure of the ß high temperature polymorph (orthorhombic, space group Pnma and unit cell parameters a=9.3118(2), b=7.0459(1), c=5.1849(1) Å has been refined. A new fluorophosphate, Na{sub 2}CdPO{sub 4}F, has been discovered and its crystal structure determined and refined from powder X-ray diffraction data. It exhibits a new 3D structure with orthorhombic symmetry, space group Pnma and unit cell parameters a=5.3731(1), b=6.8530(1),more » c=12.2691(2) Å. The structure is closely related to those of the high temperature polymorph of the nacaphite Na{sub 2}CaPO{sub 4}F and the fluorosilicate Ca{sub 2}NaSiO{sub 4}F but differs essentially in the cationic repartition since the structure is fully ordered with one Na site (8d) and one Cd site (4c). Relationships with other Na{sub 2}M{sup II}PO{sub 4}F (M{sup II}=Mg, Ca, Mn, Fe, Co, Ni) have been examined and the crystal-chemical and topographical analysis of these fluorophosphates is briefly reviewed. IR, Raman, optical and {sup 19}F, {sup 23}Na, {sup 31}P MAS NMR characterizations of Na{sub 2}CdPO{sub 4}F have been investigated. - Graphical abstract: The structure of the compound Na{sub 2}CdPO{sub 4}F, discovered during the study of the phase relationships in the NaF-CdO-NaPO{sub 3} system, has been determined and compared with other Na{sub 2}M{sup II}PO{sub 4}F fluorophosphates. - Highlights: • XRD analysis of the isothermal section of the NaF-CdO-NaPO{sub 3} system at 923 K. • Rietveld refinement of the high temperature polymorph β-NaCdPO{sub 4}. • Crystal structure of the new Na{sub 2}CdPO{sub 4}F fluorophosphate determined from powder XRD. • Crystal structure - composition relationships of Na{sub 2}M{sup II}PO{sub 4}F compounds are reviewed. • IR, Raman, optical and {sup 19}F, {sup 23}Na, {sup 31}P MAS NMR characterizations of Na{sub 2}CdPO{sub 4}F.« less

Bridgman growth of large-aperture yttrium calcium oxyborate crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Anhua, E-mail: wuanhua@mail.sic.ac.cn; Jiang, Linwen; Qian, Guoxing

2012-09-15

Highlights: ► YCOB is a novel non-linear optical crystal possessing good thermal, mechanical and nonlinear optical properties. ► Large size crystal growth is key technology question for YCOB crystal. ► YCOB crystals 3 in. in diameter were grown with modified vertical Bridgman method. ► It is a more effective growth method to obtain large size and high quality YCOB crystal. -- Abstract: Large-aperture yttrium calcium oxyborate YCa{sub 4}O(BO{sub 3}){sub 3} (YCOB) crystals with 3 in. in diameter were grown with modified vertical Bridgman method, and the large crystal plate (63 mm × 68 mm × 20 mm) was harvested formore » high-average power frequency conversion system. The crack, facet growth and spiral growth can be effectively controlled in the as-grown crystal, and Bridgman method displays more effective in obtain large size and high quality YCOB crystal plate than Czochralski technique.« less

Polyvinylpyrrolidone (PVP)-assisted solvothermal synthesis of flower-like SrCO{sub 3}:Tb{sup 3+} phosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, Yannan; Ren, Xiaolei; Zhai, Xuefeng

Graphical abstract: A simple solvothermal method for the synthesis of flower-like SrCO{sub 3}:Tb{sup 3+} phosphors with the assistance of polyvinylpyrrolidone (PVP, K30). Highlights: Black-Right-Pointing-Pointer Well-crystallized flower-like SrCO{sub 3}:Tb{sup 3+} phosphors could be easily prepared by a simple solvothermal method with the assistance of polyvinylpyrrolidone (PVP). Black-Right-Pointing-Pointer The amount of PVP and the reaction time have a strong effect on controlling the morphology and optical properties of SrCO{sub 3}:Tb{sup 3+} particles. Black-Right-Pointing-Pointer The main synthesizing process and the growth mechanism for the formation of final samples were proposed. -- Abstract: Well-crystallized flower-like SrCO{sub 3}:Tb{sup 3+} phosphors have been synthesized by anmore » inexpensive and friendly solvothermal process using polyvinylpyrrolidone (PVP, K30) as an additive without further annealing treatment. X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), and field emission scanning electron microscopy (FESEM) as well as photoluminescence spectroscopy (PL) were used to characterize the resulting samples. The amount of PVP and the reaction time have strong effect on the morphology of the SrCO{sub 3}:Tb{sup 3+} particles. The results of XRD confirm the formation of a well-crystallized SrCO{sub 3} phase with an orthorhombic structure. The possible formation mechanism for flower-like SrCO{sub 3}:Tb{sup 3+} phosphor is proposed. The SrCO{sub 3}:Tb{sup 3+} phosphors show the characteristic {sup 5}D{sub 4}-{sup 7}F{sub J} (J = 6, 5, 4, 3) emission lines with green emission {sup 5}D{sub 4}-{sup 7}F{sub 5} (544 nm) as the most prominent group under ultraviolet excitation.« less

Synthesis of mesoporous zeolite single crystals with cheap porogens

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao Haixiang; Li Changlin; Ren Jiawen

2011-07-15

Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals have been successfully synthesized by adding soluble starch or sodium carboxymethyl cellulose (CMC) to a conventional zeolite synthesis system. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen sorption analysis, {sup 27}Al magic angle spinning nuclear magnetic resonance ({sup 27}Al MAS NMR), temperature-programmed desorption of ammonia (NH{sub 3}-TPD) and ultraviolet-visible spectroscopy (UV-vis). The SEM images clearly show that all zeolite crystals possess the similar morphology with particle size of about 300 nm, the TEM images reveal that irregular intracrystalmore » pores are randomly distributed in the whole crystal. {sup 27}Al MAS NMR spectra indicate that nearly all of the Al atoms are in tetrahedral co-ordination in ZSM-5, UV-vis spectra confirm that nearly all of titanium atoms are incorporated into the framework of TS-1. The catalytic activity of meso-ZSM-5 in acetalization of cyclohexanone and meso-TS-1 in hydroxylation of phenol was also studied. The synthesis method reported in this paper is cost-effective and environmental friendly, can be easily expended to prepare other hierarchical structured zeolites. - Graphical abstract: Mesoporous zeolite single crystals were synthesized by using cheap porogens as template. Highlights: > Mesoporous zeolite (silicalite-1, ZSM-5, TS-1) single crystals were synthesized. > Soluble starch or sodium carboxymethyl cellulose (CMC) was used as porogens. > The mesoporous zeolites had connected mesopores although closed pores existed. > Higher catalytic activities were obtained.« less

Age differences in relationships between crystallized and fluid intelligences and problem solving.

PubMed

Hayslip, B; Sterns, H L

1979-05-01

One hundred and sixty-two subjects at three age levels were tested to examine the relationship between crystallized (Gc) and fluid (Gf) abilities and three problem solving tasks varying in the abstractness concreteness of their stimuli and emphasis on past experience. It was predicted that the difference in correlations between crystallized and fluid abilities and each of these tasks would increase with increased age. The hypotheses were partially supported in the young and elderly groups of subjects. On tasks using concrete stimuli, emphasizing past experience, where no cross-sectional decline was observed, Gc (relative to Gf) accounted for an increasing proportion of variance in performance with increased age. On tasks using abstract stimuli, de-emphasizing past experience, where significant cross-sectional declines were obtained, Gf (relative to Gc) correlated more highly with performance. Contrary to previous research, relationships between Gf and Bc supported a reintegration of abilities in old age.

Synthesis, structure, and magnetic characterization of Cr{sub 4}US{sub 8}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Matthew D.; Chan, Ian Y.; Malliakas, Christos D.

The compound Cr{sub 4}US{sub 8} has been synthesized at 1073 K and its crystal structure has been determined at 100 K. The structure is modulated with a two-fold commensurate supercell. The subcell may be indexed in an orthorhombic cell but weak supercell reflections lead to the monoclinic superspace group P2{sub 1}/c(α0γ)0s with two Cr sites, one U site, and four S sites. The structure comprises a three-dimensional framework of CrS{sub 6} octahedra with channels that are partially occupied by U atoms. Each U atom in these channels is coordinated by eight S atoms in a bicapped trigonal-prismatic arrangement. The magneticmore » behavior of Cr{sub 4}US{sub 8} is complex. At temperatures above ~120 K at all measured fields, there is little difference between field-cooled and zero field-cooled data and χ(T) decreases monotonously with temperature, which is reminiscent of the Curie–Weiss law. At lower temperatures, the temperature dependence of χ(T) is complex and strongly dependent on the magnetic field strength. - Graphical abstract: Structure of Cr{sub 4}US{sub 8} viewed down the a axis. - Highlights: • At 1073 K Cr{sub 4}US{sub 8} was synthesized and at 100 K its crystal structure was determined. • The 3D structure comprises CrS{sub 6} octahedra with channels partially occupied by U. • The magnetic behavior of Cr{sub 4}US{sub 8} is complex.« less

Synthesis of core–shell structured FAU/SBA-15 composite molecular sieves and their performance in catalytic cracking of polystyrene

PubMed Central

Du, Jinlong; Shi, Chunwei; Wu, Wenyuan; Bian, Xue; Chen, Ping; Cui, Qingzhu; Cui, Zhixuan

2017-01-01

Abstract Composite molecular sieves, FAU/SBA-15, having core-shell structure were synthesized. The synthesized composite sieves were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), pyrolysis fourier transform infrared (Py-FTIR) spectroscopy, temperature programmed desorption spectra (NH3-TPD), UV Raman spectroscopy, nuclear magnetic resonance (NMR) and other techniques. XRD, SEM, TEM, N2 adsorption-desorption, mass spectrometry, NMR and EDS results showed that the composite molecular sieve contained two pore channels. Py-FTIR results showed that the addition of HY molecular sieves improved the acidity of the composite zeolite. The crystallization mechanism during the growth of FAU/SBA-15 shell was deduced from the influence of crystallization time on the synthesis of FAU/SBA-15 core-shell structured composite molecular sieve. HY dissociated partially in H2SO4 solution, and consisted of secondary structural units. This framework structure was more stable than its presence in the isolated form on the same ring or in the absence of Al. Thus it played a guiding role and connected with SBA-15 closely through the Si-O bond. This resulted in the gradual covering of the exterior surface of FAU phase by SBA-15 molecular sieves. The presence of SBA-15 restricted the formation of the other high mass components and increased the selectivity towards ethylbenzene. PMID:29383044

Boric acid flux synthesis, structure and magnetic property of MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Dingfeng; Cong, Rihong; Gao, Wenliang, E-mail: gaowl@cqu.edu.cn

2013-05-01

Three new borates MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn) have been synthesized by boric acid flux methods, which are isotypic to NiB₁₂O₁₄(OH)₁₀. Single-crystal XRD was performed to determine the crystal structures in detail. They all crystallize in the monoclinic space group P2₁/c. The size of MO{sub 6} (M=Mg, Mn, Fe, Co, Ni, Zn) octahedron shows a good agreement with the Shannon effective ionic radii of M²⁺. Magnetic measurements indicate MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering down to 2 K. The values of its magnetic superexchange constants were evaluated by DFT calculations, which explain the observed magnetic behavior. The UV–vis diffuse reflectancemore » spectrum of ZnB₁₂O₁₄(OH)₁₀ suggests a band gap ~4.6 eV. DFT calculations indicate it has a direct band gap 4.9 eV. The optical band gap is contributed by charge transfers from the occupied O 2p to the unoccupied Zn 4s states. - Graphical abstract: Experimental and theoretical studies indicate MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering. DFT calculations show ZnB₁₂O₁₄(OH)₁₀ has a direct band gap of 4.9 eV. Highlights: • MB₁₂O₁₄(OH)₁₀ (M=Mn, Fe, Zn) are synthesized by two-step boric acid flux method. • Single-crystal XRD was performed to determine the crystal structures in detail. • Size of MO₆ (M=Mg, Mn, Fe, Co, Ni, Zn) agrees with the effective ionic radii. • MnB₁₂O₁₄(OH)₁₀ is antiferromagnetic without a long-range ordering down to 2 K. • DFT calculations indicate ZnB₁₂O₁₄(OH)₁₀ has a direct band gap 4.9 eV.« less

Ribbon Growth of Single Crystal GaAs for Solar Cell Application.

DTIC Science & Technology

1981-11-01

Entered) 20. Abstract (Cont.) 7growth techniques, dendrite seeds, and melt chemistry were optimized during the course of the program; however...Faceted Web. 10 Crystal Grown From a Melt Doped With 1.0 Atomic% Ge. 17 The Ge-Doped Crystals Grew at Low Undercooling and Contained Flatter Textured-Web...Ge Melt Doping. The 18 Textured-Web Sections Were the Widest Achieved at Small Undercooling, ɝ.0°C. 12 Radiation Exchange Between the Melt Surface

Research Support for the Laboratory for Lightwave Technology

DTIC Science & Technology

1992-12-31

34 .. . ."/ 12a. DISTRIBUTION AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE UNLIMITED 13. ABSTRACT (Mawimum 200words) 4 SEE ATTACHED ABSTRACT DT I 14. SUBJECT...8217TERMS 15. NUMBER OF PAGES 16. PRICE CODE 17. SECURITY CLASSIFICATION 18. SECURITY CLASSIFICATION 19. SECURITY CLASSIFICATION 20. LIMITATION OF ABSTRACT...temperature ceramic nano- phase single crystal oxides that may be produced at a high rate . The synthesis of both glasses and ceramics using novel techniques

X-ray evaluation of crystals for stellar spectrometers

NASA Technical Reports Server (NTRS)

Alexandropolos, N. G. (Editor)

1974-01-01

The report consists of three parts. The first part is an analysis of the principles involved in X-ray crystal evaluation and how they are applied to a number of crystals. The principles of crystal evaluation analysis as they apply to the special problems of X-ray astronomy are presented. A number of crystals were evaluated, and the energy dependence of the diffraction properties of (002) PET, (111) Ge, (101) ADP, (001) KAP, and (001) RAP are reported. The second part is a compilation of the diffraction properties of a number of crystals as reported by other authors. In the third part some technical details of a triple crystal spectrometer built by the author at Polytechnic Institute of Brooklyn are given. This spectrometer seems to be a most appropriate instrument for evaluation of crystal properties. (Modified author abstract)

Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Kovrugin, Vadim M.; Tyumentseva, Olga S.

2015-09-15

Single crystals of seven novel uranyl oxysalts of selenium with protonated methylamine molecules, [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)] (I), [C{sub 2}H{sub 8}N]{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O)] (II), [C{sub 4}H{sub 15}N{sub 3}][H{sub 3}O]{sub 0.5}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 2.93}(SeO{sub 3}){sub 0.07}(H{sub 2}O)](NO{sub 3}){sub 0.5} (III), [C{sub 2}H{sub 8}N]{sub 3}[H{sub 5}O{sub 2}][(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub 2}(H{sub 2}O){sub 5} (IV), [C{sub 2}H{sub 8}N]{sub 2}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 4}(HSeO{sub 3})(H{sub 2}O)](H{sub 2}SeO{sub 3}){sub 0.2} (V), [C{sub 4}H{sub 12}N]{sub 3}[H{sub 3}O][(UO{sub 2}){sub 3}(SeO{sub 4}){sub 5}(H{sub 2}O)] (VI), and [C{sub 2}H{sub 8}N]{sub 3}(C{sub 2}H{sub 7}N)[(UO{sub 2}){sub 3}(SeO{sub 4}){submore » 4}(HSeO{sub 3})(H{sub 2}O)] (VII) have been prepared by isothermal evaporation from aqueous solutions. Their crystal structures have been solved by direct methods and their uranyl selenate and selenite–selenate units investigated using black-and-white graphs from the viewpoints of topology of interpolyhedral linkages and isomeric variations. The crystal structure of IV is based upon complex layers with unique topology, which has not been observed previously in uranyl selenates. Investigations of the statistics and local distribution of the U–O{sub br}–Se bond angles demonstrates that shorter angles associate with undulations, whereas larger angles correspond to planar areas of the uranyl selenite layers. - Graphical abstract: Crystal structures of the seven novel Se-contaning uranyl oxysalts that contain protonated organic molecules as interlayer species have been investigated from the viewpoints of topology of interpolyhedral linkages, isomeric variations and flexibility of structural units. - Highlights: • Single crystals of seven novel uranyl oxysalts were prepared by evaporation method. • The graph theory was used for investigation of topologies of structural units. • The method of orientation matrices was applied to distinguish geometrical isomers. • The flexibility of structural complexes specifies the undulation of layered structural units.« less

Synthesis, XRD crystal structure, spectroscopic characterization, local reactive properties using DFT and molecular dynamics simulations and molecular docking study of (E)-1-(4-bromophenyl)-3-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one

NASA Astrophysics Data System (ADS)

Arshad, Suhana; Raveendran Pillai, Renjith; Zainuri, Dian Alwani; Khalib, Nuridayanti Che; Razak, Ibrahim Abdul; Armaković, Stevan; Armaković, Sanja J.; Renjith, Rishikesh; Panicker, C. Yohannan; Van Alsenoy, C.

2017-06-01

In the present study, the title compound named as (E)-1-(4-bromophenyl)-3-(4-(trifluoromethoxy)phenyl)prop-2-en-1-one was synthesized and structurally characterized by single-crystal X-ray diffraction. The FT-IR spectrum was recorded and interpreted in details with the aid of Density Functional Theory (DFT) calculations and Potential Energy Distribution (PED) analysis. Average local ionization energies (ALIE) and Fukui functions have been used as quantum-molecular descriptors to locate the molecule sites that could be of importance from the aspect of reactivity. Degradation properties have been assessed by calculations of bond dissociation energies (BDE) for hydrogen abstraction and the rest of the single acyclic bonds, while molecular dynamics (MD) simulations were used in order to calculate radial distribution functions and determine the atoms with significant interactions with water. In order to understand how the title molecule inhibits and hence increases the catalytic efficiency of MOA-B enzyme, molecular docking study was performed to fit the title compound into the binding site of MOA-B enzyme.

Field-Effects in Large Axial Ratio Liquid Crystals

NASA Astrophysics Data System (ADS)

Lonberg, Franklin J.

This paper consists of an introduction and four chapters, the abstracts of which are presented below. Chapter 2. The subject of this chapter is the dynamic periodic structures which are observed in the twist Frederiks transition. It is found that, for fields above a material dependent level, a transient periodic distortion is observed. The wave vector is parallel to the unperturbed director and increases with increasing field. A theoretical model and experimental data are presented. Chapter 3. The subject of this chapter is the discovery of a new equilibrium structure in the splay Frederiks transition. Experimental observation has shown that the imposition of a field, just above the critical strength, produces a periodic distortion in the polymer liquid crystal PBG. This periodic state is not dynamic in origin but it is a true ground state. An analysis of the energy of a liquid crystal, in the splay Frederiks transition geometry, shows that in materials with K(,1)/K(,3) > 3.3 the periodic distortion will have a lower critical field than the uniform distortion. Chapter 4. The subject of this chapter is the dynamics of the bend Frederiks transition in large axial ratio nematics. Experimental evidence is presented to show that there is a distortion mode which occurs at field greater than 2H(,c), which is very fast and does not grow exponentially. An analysis of the equations of motion shows that a mode with wave length half that of the static equilibrium mode will have these properties. Chapter 5. The bend Frederiks transition is use to show that the bend and splay elastic constants are linear in concentration in PBG. Interpretation of this result is made in connection with models of the elastic energy in liquid crystal made of semi-flexible partiles.

Design and realization of transparent solar modules based on luminescent solar concentrators integrating nanostructured photonic crystals

PubMed Central

Jiménez‐Solano, Alberto; Delgado‐Sánchez, José‐Maria; Calvo, Mauricio E.; Miranda‐Muñoz, José M.; Lozano, Gabriel; Sancho, Diego; Sánchez‐Cortezón, Emilio

2015-01-01

Abstract Herein, we present a prototype of a photovoltaic module that combines a luminescent solar concentrator integrating one‐dimensional photonic crystals and in‐plane CuInGaSe2 (CIGS) solar cells. Highly uniform and wide‐area nanostructured multilayers with photonic crystal properties were deposited by a cost‐efficient and scalable liquid processing amenable to large‐scale fabrication. Their role is to both maximize light absorption in the targeted spectral range, determined by the fluorophore employed, and minimize losses caused by emission at angles within the escape cone of the planar concentrator. From a structural perspective, the porous nature of the layers facilitates the integration with the thermoplastic polymers typically used to encapsulate and seal these modules. Judicious design of the module geometry, as well as of the optical properties of the dielectric mirrors employed, allows optimizing light guiding and hence photovoltaic performance while preserving a great deal of transparency. Optimized in‐plane designs like the one herein proposed are of relevance for building integrated photovoltaics, as ease of fabrication, long‐term stability and improved performance are simultaneously achieved. © 2015 The Authors. Progress in Photovoltaics: Research and Applications published by John Wiley & Sons Ltd. PMID:27656090

Synthesis, crystal structure, and magnetic properties of quaternary iron selenides: Ba{sub 2}FePnSe{sub 5} (Pn=Sb, Bi)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jian; Greenfield, Joshua T.; Kovnir, Kirill

Two new barium iron pnictide–selenides, Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5}, were synthesized by a high-temperature solid-state route and their crystal structures were determined using single crystal X-ray diffraction. Both compounds are isomorphic to the high pressure phase Ba{sub 3}FeS{sub 5} and crystallize in the orthorhombic space group Pnma (No. 62) with cell parameters of a=12.603(2)/12.619(2) Å, b=9.106(1)/9.183(1) Å, c=9.145(1)/9.123(1) Å and Z=4 for Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5}, respectively. According to differential scanning calorimetry, Ba{sub 2}FePnSe{sub 5} compounds exhibit high thermal stability and melt congruently at 1055(5) K (Pn=Sb) and 1105(5) K (Pn=Bi). Magnetic characterizations revealmore » strong antiferromagnetic nearest-neighbor interactions in both compounds resulting in an antiferromagnetic ordering at 58(1) K for Ba{sub 2}FeSbSe{sub 5} and 79(2) K for Ba{sub 2}FeBiSe{sub 5}. The magnetic interactions between Fe{sup 3+} centers, which are at least 6 Å apart from each other, are mediated by superexchange interactions. - Graphical abstract: In Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} the magnetic interactions between Fe{sup 3+} centers, which are at least 6 Å apart from each other, are mediated by superexchange interactions. - Highlights: • New compounds Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} have been synthesized. • The crystal structure was determined by single crystal X-ray diffraction. • Both compounds melt congruently at temperatures above 1000 K. • Ba{sub 2}FeSbSe{sub 5} and Ba{sub 2}FeBiSe{sub 5} exhibit AFM ordering at 58 K (Sb) and 70 K (Bi). • Magnetic exchange between Fe{sup 3+} is mediated by either Se–Sb(Bi)–Se or Se–Ba–Se bridges.« less

Abstracts, Third Space Processing Symposium, Skylab results

NASA Technical Reports Server (NTRS)

1974-01-01

Skylab experiments results are reported in abstracts of papers presented at the Third Space Processing Symposium. Specific areas of interest include: exothermic brazing, metals melting, crystals, reinforced composites, glasses, eutectics; physics of the low-g processes; electrophoresis, heat flow, and convection demonstrations flown on Apollo missions; and apparatus for containerless processing, heating, cooling, and containing materials.

AN FT-IR STUDY OF NO 2 REDUCTION IN NANOCRYSTALLINE NAY SEOLITE: EFFECT OF ZEOLITE CRYSTAL SIZE AND ADSORBED WATER. (R829600)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Crystal structure studies of NADP{sup +} dependent isocitrate dehydrogenase from Thermus thermophilus exhibiting a novel terminal domain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, S.M.; Pampa, K.J.; Manjula, M.

2014-06-20

Highlights: • We determined the structure of isocitrate dehydrogenase with citrate and cofactor. • The structure reveals a unique novel terminal domain involved in dimerization. • Clasp domain shows significant difference, and catalytic residues are conserved. • Oligomerization of the enzyme is quantized with subunit-subunit interactions. • Novel domain of this enzyme is classified as subfamily of the type IV. - Abstract: NADP{sup +} dependent isocitrate dehydrogenase (IDH) is an enzyme catalyzing oxidative decarboxylation of isocitrate into oxalosuccinate (intermediate) and finally the product α-ketoglutarate. The crystal structure of Thermus thermophilus isocitrate dehydrogenase (TtIDH) ternary complex with citrate and cofactor NADP{supmore » +} was determined using X-ray diffraction method to a resolution of 1.80 Å. The overall fold of this protein was resolved into large domain, small domain and a clasp domain. The monomeric structure reveals a novel terminal domain involved in dimerization, very unique and novel domain when compared to other IDH’s. And, small domain and clasp domain showing significant differences when compared to other IDH’s of the same sub-family. The structure of TtIDH reveals the absence of helix at the clasp domain, which is mainly involved in oligomerization in other IDH’s. Also, helices/beta sheets are absent in the small domain, when compared to other IDH’s of the same sub family. The overall TtIDH structure exhibits closed conformation with catalytic triad residues, Tyr144-Asp248-Lys191 are conserved. Oligomerization of the protein is quantized using interface area and subunit–subunit interactions between protomers. Overall, the TtIDH structure with novel terminal domain may be categorized as a first structure of subfamily of type IV.« less

Crystal structure and biochemical characterization of beta-keto thiolase B from polyhydroxyalkanoate-producing bacterium Ralstonia eutropha H16

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Eun-Jung; Son, Hyeoncheol Francis; Kim, Sangwoo

Highlights: • We determined a crystal structure of β-keto thiolase from Ralstonia eutropha H16 (ReBktB). • Distinct substrate binding mode ReBktB was elucidated. • Enzymatic kinetic parameters of ReBktB were revealed. - Abstract: ReBktB is a β-keto thiolase from Ralstonia eutropha H16 that catalyzes condensation reactions between acetyl-CoA with acyl-CoA molecules that contains different numbers of carbon atoms, such as acetyl-CoA, propionyl-CoA, and butyryl-CoA, to produce valuable bioproducts, such as polyhydroxybutyrate, polyhydroxybutyrate-hydroxyvalerate, and hexanoate. We solved a crystal structure of ReBktB at 2.3 Å, and the overall structure has a similar fold to that of type II biosynthetic thiolases, suchmore » as PhbA from Zoogloea ramigera (ZrPhbA). The superposition of this structure with that of ZrPhbA complexed with CoA revealed the residues that comprise the catalytic and substrate binding sites of ReBktB. The catalytic site of ReBktB contains three conserved residues, Cys90, His350, and Cys380, which may function as a covalent nucleophile, a general base, and second nucleophile, respectively. For substrate binding, ReBktB stabilized the ADP moiety of CoA in a distinct way compared to ZrPhbA with His219, Arg221, and Asp228 residues, whereas the stabilization of β-mercaptoethyamine and pantothenic acid moieties of CoA was quite similar between these two enzymes. Kinetic study of ReBktB revealed that K{sub m}, V{sub max}, and K{sub cat} values of 11.58 μM, 1.5 μmol/min, and 102.18 s{sup −1}, respectively, and the catalytic and substrate binding sites of ReBktB were further confirmed by site-directed mutagenesis experiments.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cano, A.; Osiry, H.; Reguera, L.

The titled compound was prepared by the precipitation method from diluted aqueous solution of sodium nitroprusside and mercury(II) nitrate. The orange solid formed, with formula unit Hg[Fe(CN){sub 5}NO], crystallizes with an orthorhombic unit cell in the Pmna space group with cell parameters: a=11.2788(3), b=6.1965(3), and c=12.3786(6) Å. The unit cell accommodates four formula of the compound (Z=4). Its crystal structure was solved from X-ray powder patterns and then refined by the Rietveld method. The material framework is formed by tetrahedral coordination of Hg atoms at the N end of the equatorial CN groups of the [Fe(CN){sub 5}NO] building block. Thatmore » framework results from the interpenetration of two identical sub-frameworks with a relative shift of (a/2, b/2, c/2). The sub-framework has two types of cavities, ellipsoidal and rhombohedral, with transversal section of ca. 4.5×9.2 Å and ca. 8.5 Å transversal section, respectively. That system of cavities results eclipsed by the relative shift of neighboring sub-frameworks. No transport of H{sub 2} and N{sub 2} molecules through the material framework was observed. The thermal decomposition also reveals limitation for the decomposition products diffusion through the practically compact structure. The structural study was complemented with TG, IR, UV–vis and N{sub 2} and H{sub 2} adsorption data. Neighboring Hg atoms are distant 4.54(3) Å, a relatively large distance to suppose the existence of metal–metal interaction. No previous study on the crystal structure and related properties of mercury(II) nitroprusside has been reported. - Graphical abstract: Mercury(II) nitroprusside framework formed by two identical interpenetrated porous subframeworks where neighboring cavities appear eclipsed. - Highlights: • Interpenetrated frameworks in metal nitroprusside. • Eclipsed porous framework in metal nitroprusside. • Structure and related properties for mercury(II) nitroprusside. • Spectral features for mercury(II) nitroprusside.« less

Coordination polymers with the chiral ligand N-p-tolylsulfonyl-L-glutamic acid: Influence of metal ions and different bipyridine ligands on structural chirality

DOE Office of Scientific and Technical Information (OSTI.GOV)

He Rong; Song Huihua, E-mail: songhuihua@mail.hebtu.edu.c; Wei Zhen

2010-09-15

Four new polymers, namely [Ni(-tsgluO)(2,4'-bipy){sub 2}(H{sub 2}O){sub 2}]{sub n}.5nH{sub 2}O (1), [Co(-tsgluO)(2,4'-bipy){sub 2}(H{sub 2}O){sub 2}]{sub n}.5nH{sub 2}O (2), [Ni(-tsgluO)(4,4'-bipy)]{sub n}.0.5nH{sub 2}O (3), and [Co(-tsgluO)(4,4'-bipy)]{sub n}.0.5nH{sub 2}O (4), where tsgluO{sup 2-}=(+)-N-p-tolylsulfonyl-L-glutamate dianion, 2,4'-bipy=2,4'-bipyridine, and 4,4'-bipy=4,4'-bipyridine, have been prepared and structurally characterized. Compounds 1 and 2 are isostructural and mononuclear, and crystallize in the acentric monoclinic space group Cc, forming 1D chain structures. Compound 3 is also mononuclear, but crystallizes in the chiral space group P2{sub 1}, forming a homochiral 2D architecture. In contrast to the other complexes, compound 4 crystallizes in the space group P-1 and is composed of binuclear [Co{submore » 2}O{sub 6}N{sub 2}]{sub n}{sup 4-} units, which give rise to a 2D bilayer framework. Moreover, compounds 1, 2, and 4 self-assemble to form 3D supramolecular structures through {pi}-{pi} stacking and hydrogen-bonding interactions, while compound 3 is further hydrogen-bonded to form 3D frameworks. We have demonstrated the influence of the central metal and bipyridine ligands on the framework chirality of the coordination complexes. - Graphical abstract: Four novel polymers based on a chiral ligand were prepared and structurally characterized; it represents the first series of investigations about the effect of central metals and bipyridine ligands on framework chirality.« less

Porous framework of T{sub 2}[Fe(CN){sub 6}].xH{sub 2}O with T=Co, Ni, Cu, Zn, and H{sub 2} storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Avila, M.; Reguera, L.; Rodriguez-Hernandez, J.

2008-11-15

The materials under study were prepared from aqueous solutions of ferrocyanic acid and salts of the involved transition metals and their crystal structure solved and refined from X-ray powder diffraction data. Complementary information from thermogravimetric, infrared and Moessbauer data was also used for the structural study. Three different crystal structures were found: hexagonal (P-3) for Zn with the zinc atom coordinated to three N ends of CN groups plus a water molecule, cubic (Pm-3m) for Ni and Cu, and monoclinic (P2{sub 1}/m) for Co. For Ni and Cu the obtained solids have an open channel framework related to 50% ofmore » vacancies for the building unit, [Fe(CN){sub 6}]. In the as-synthesized material the framework free volume is occupied by coordinated and hydrogen-bonded water molecules. These of hexacyanoferrates (II) have received certain attention as prototype of materials for the hydrogen storage. In the anhydrous phase of Ni and Cu, 50% of the metal (T) coordination sites, located at the cavities surface, will be available to interact with the hydrogen molecule. However, when the crystal waters are removed the porous frameworks collapse as it is suggested by H{sub 2} and CO{sub 2} adsorption data. For Co, a structure of stacked layers was found where the cobalt atoms have both tetrahedral and octahedral coordination. The layers remain together through a network of hydrogen-bonding interactions between coordinated and weakly bonded water molecules. No H{sub 2} adsorption was observed in the anhydrous phase of Co. For Zn, the porous framework remains stable on the water removal but with a system of narrow channels and a small available volume, also inaccessible to H{sub 2}. - Graphical abstract: Structure of stacked layers for CO{sub 2}[Fe(CN){sub 6}].xH{sub 2}O.« less

Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keates, Adam C.; Wang, Qianlong; Weller, Mark T., E-mail: m.t.weller@bath.ac.uk

2014-02-15

Single crystal and bulk polycrystalline forms of K{sub 2}MP{sub 2}O{sub 7} (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42{sub 1}m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP{sub 2}O{sub 7}]{sup 2−} with potassium cations situated between the layers. The MO{sub 4} tetrahedra share oxygen atoms with [P{sub 2}O{sub 7}]{sup 4−} diphosphate groups and the potassium ions have KO{sub 8} square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen,more » as a result of the Jahn–Teller (JT) effect for the high spin d{sup 6} Fe(II) and p-orbital mixing or a second order JT effect for d{sup 9} Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K{sub 2}MP{sub 2}O{sub 7}, M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP{sub 2}O{sub 7}]{sup 2−}, formed from linked pyrophosphate groups and MO{sub 4} tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d{sup 6} Fe(II) and p-orbital mixing and second-order JT effects for d{sup 9} Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d{sup 10} distorted coordinations.« less

The new Zintl phases Eu{sub 21}Cd{sub 4}Sb{sub 18} and Eu{sub 21}Mn{sub 4}Sb{sub 18}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yi; Darone, Gregory M.; Bobev, Svilen, E-mail: bobev@udel.edu

Crystals of two new Zintl compounds, Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} have been synthesized using the molten metal flux method, and their structures have been established by single-crystal X-ray diffraction. Both compounds are isotypic and crystallize in the monoclinic space group C2/m (No. 12, Z=4). The structures are based on edge- and corner-shared MnSb{sub 4} or CdSb{sub 4} tetrahedra, which make octameric [Mn{sub 8}Sb{sub 22}] or [Cd{sub 8}Sb{sub 22}] polyanions. Homoatomic Sb–Sb bonds are present in both structures. The Eu atoms take the role of Eu{sup 2+}cations with seven unpaired 4f electrons, as suggested by themore » temperature-dependent magnetization measurements. The magnetic susceptibilities of Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} indicate that both phases order anti-ferromagnetically with Néel temperatures of ca. 7 K and ca. 10 K, respectively. The unpaired 3d electrons of the Mn atoms in Eu{sub 21}Mn{sub 4}Sb{sub 18} do contribute to the magnetic response, however, the bulk magnetization measurements do not provide evidence for long-range ordering of the Mn spins down to 5 K. Electrical resistivity measurements suggest that both compounds are narrow band gap semiconductors. - Graphical abstract: Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} have complex monoclinic structures, based on MnSb{sub 4} and CdSb{sub 4} tetrahedra, both edge- and corner-shared. A perspective of the crystal structure is shown, as viewed along the b axis. Display Omitted - Highlights: • Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} are novel compounds in the respective ternary phase diagrams. • For both structures, the Zintl-Klemm rules are followed, and both are small gap semiconductors. • Eu{sub 21}Mn{sub 4}Sb{sub 18} and Eu{sub 21}Cd{sub 4}Sb{sub 18} are air-stable Zintl phases and could be new thermoelectric materials.« less

TEM study of the (SbS){sub 1+δ}(NbS{sub 2}){sub n}, (n=1, 2, 3; δ~1.14, 1.20) misfit layer phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gómez-Herrero, A., E-mail: adriangh@pdi.ucm.es; Landa-Cánovas, A.R.; Otero-Díaz, L.C.

In the Sb–Nb–S system four new misfit layer phases have been found and carefully investigated via Transmission Electron Microscopy (TEM). Their structures are of composite modulated structure type with stoichiometries that can be formulated as (SbS){sub 1+δ}(NbS{sub 2}){sub n}; for n=1, δ~1.14 and 1.19; for n=2, δ~1.18 and for n=3, δ~1.19. Selected Area Electron Diffraction (SAED) patterns show an almost commensurate fit between the pseudo-tetragonal (SbS) and the pseudo-orthohexagonal (NbS{sub 2}){sub n} subcells along the misfit direction a, with 3(SbS)≈5(NbS{sub 2}), being b the same for both sub-lattices and c the stacking direction. For n=1, a commensurate phase with 4a{submore » SbS}=7a{sub NbS2} has also been observed. In addition to the characteristic misfit and associated modulation of the two sub-structures, a second modulation is also present which appears to be primarily associated with the (SbS) sub-structure of both the n=1 and n=2 phases. High Resolution Transmission Electron Microscopy (HRTEM) images show ordered stacking sequences between the (SbS) and (NbS{sub 2}){sub n} lamellae for each of the four phases, however, disordered intergrowths were also occasionally found. Most of the crystals showed different kinds of twinning defects on quite a fine scale. Many crystals showed curled up edges. In some cases the lamellar crystals were entirely folded giving rise to similar diffraction patterns as found for cylindrical crystals. - Graphical abstract: Idealized structure models of the first three members of the homologous series (SbS){sub 1+δ}(NbS{sub 2}){sub n}. - Highlights: • Transmission Electron Microscopy study of misfit layer sulfides (SbS){sub 1+δ}(NbS{sub 2}){sub n}. • The structures consist of a (SbS) layer interleaved between n (NbS{sub 2}) layers. • Two different members n=1, one n=2 and one n=3 have been studied. • Twinning, intergrowths and different modulations in the (SbS) substructure.« less

Syntheses, structures and properties of two new coordination polymers based on D-camphoric acid and 2-phenyl-4,6-diamino-1,3,5-triazine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lun, Huijie; Yang, Jinghe; Jin, Linyu

2015-05-15

By hydrothermal method, two new coordination polymers [Co(ca)(phdat)]{sub n} (1), [Ni(ca)(phdat).0.125H{sub 2}O]{sub n} (2) (H{sub 2}ca=D-camphoric acid, phdat=2-phenyl-4,6-diamino-1,3,5-triazine) have been achieved and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isostructural, both of which exhibit two-dimensional layered network built up from paddle-wheel Co{sub 2}(CO{sub 2}){sub 4}/Ni{sub 2}(CO{sub 2}){sub 4} SBUs by ca{sup 2−} ligand. In the existence of π…π stacking interactions between triazine rings and phenyl rings, the 3D networks are constructed with the hanging phdat filled between the neighboring layers. Furthermore, compounds 1–2 exhibit antiferromagneticmore » behavior and compound 2 displays a good activity for methanol oxidation. - Graphical abstract: Two new coordination compounds 1–2 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses, magnetic and electrochemical measurement. - Highlights: • This paper reports two new coordination polymers based on D-camphoric acid. • Both the compounds feather two-dimensional layered networks built up from paddle-wheel SBUs. • The magnetism and electrochemical property are investigated.« less

Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27}: Solid-state synthesis, crystal structure and site-preference

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jeon, Beom-Yong; Nam, Gnu; Lee, Dong Woo

A novel intermetallic compound of Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27} has been synthesized through the high-temperature solid-state reaction using Nb-ampoules. A batch of well grown block-/short bar-shaped single-crystals has been obtained, and the crystal structure of the title compound has been characterized by single-crystal X-ray diffraction analyses. Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27} adopts the Ho{sub 11}Ge{sub 10}-type structure belonging to the tetragonal space group I4/mmm (Z=4, Pearson symbol tI84) with nine crystallographically unique atomic positions in the asymmetric unit. The lattice parameters are a=12.0163(1) Å and c=16.5396(2) Å. The overall crystal structure can simply be depicted as an assembly of three differentmore » types of co-facial cationic polyhedra centered by anions, which is further enclosed by the three-dimensional (3-D) cage-like anionic framework. The extra amount of In is observed in one of three isolated anionic sites resulting in introducing the Ge/In-mixed site at the Wyckoff 4e site. This unique site-preference of In substitution for Ge at the 4e site has been enlightened via the atomic size-aspect which was fully supported and rationalized by the site- and bond-energies analyses using tight-binding linear muffin-tin orbital (TB-LMTO) calculations. Energy-dispersive X-ray spectroscopy (EDS), density of states (DOS), crystal orbital Hamilton population (COHP), and electron localization function (ELF) analyses for the title compound are also presented. Magnetic susceptibility measurement proves that an antiferromagnetic ordering of Ce atoms at a low temperature with a paramagnetic Curie temperature of −23.2 K. - Graphical abstract: Reported is experimental and theoretical investigations for Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27}, which is the first reported example having the extra amounts of In substitution for Ge at one of three “isolated” anionic sites in the Ho{sub 11}Ge{sub 10}-type phase. The observed In site-preference toward the particular anionic site was rationalized via the atomic size-aspect supported by comprehensive analyses for the site-energies including the Wyckoff 4e and 8j sites. - Highlights: • Block or short-bar shaped single-crystals of Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27} were synthesized. • The first example of having the In/Ge mixture at the “isolated” anionic site. • The site-preference of In was rationalized by the site- and bond-energies.« less

Crystallization Experiments of the Martian Meteorite QUE94201: Additional Constraints on Its Formation Condition

NASA Technical Reports Server (NTRS)

Koizumi, E.; McKay, G.; Mikouchi, T.; Le, L.; Schwandt, C.; Monkawa, A.; Miyamoto, M.

2002-01-01

We focused on the Al/Ti ratio in synthetic pyroxenes as a marker for the onset of plagioclase crystallization and discuss the effects of oxygen fugacity on the Kd(Fe/Mg)ol/gl in our experiments using the same composition of QUE94201. Additional information is contained in the original extended abstract.

Age Differences in Relationships Between Crystallized and Fluid Intelligences and Problem Solving.

ERIC Educational Resources Information Center

Hayslip, Bert, Jr.; Sterns, Harvey L.

One hundred and sixty-two subjects of three age levels were tested to examine the relationship between crystallized and fluid abilities and three problem solving tasks varying in the abstractness/concreteness of their stimuli and emphasis on past experience. These dimensions have been used by Davis to distinguish between Type "O" and Type "C"…

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silva, Camila F.N.; Lazarin, Angélica M., E-mail: amlazarin2@uem.br; Sernaglia, Rosana L.

Graphical abstract: Scanning electron microscopy photographs of calcium phosphate (a) and intercalated with p-aminobenzoic acid (b). Highlights: ► Calcium phosphate was intercalated with p-aminobenzoic acid. ► Guest molecule contains nitrogen and oxygen atoms from amine and carboxylic groups. ► These basic centers are potentially useful for cation coordination in ethanol solution. ► Crystal morphology of compounds is lamellar, it agrees with expected structural characteristics. -- Abstract: Crystalline lamellar calcium phosphate retained 4-aminobenzoic acid inside its cavity without leaching. The intense infrared bands in the 1033 and 1010 cm{sup −1} interval confirmed the presence of the phosphonate groups attached to themore » inorganic layer, with sharp and intense peaks in X-ray diffraction patterns, which gave basal distances of 712 and 1578 pm for the original and the intercalated compounds, respectively. Solid-state {sup 31}P nuclear magnetic resonance spectra presented only one peak for the phosphate groups attached to the main inorganic polymeric structure near −2.4 ppm. The adsorption isotherms from ethanol gave the maximum adsorption capacities of 6.44 and 3.34 mmol g{sup −1} for nickel and cobalt, respectively, which stability constant and distribution coefficient followed Co > Ni.« less

New vanadium tellurites: Syntheses, structures, optical properties of noncentrosymmetric VTeO{sub 4}(OH), centrosymmetric Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Ming-Li; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002; Marsh, Matthew

Two new vanadium tellurites, VTeO{sub 4}(OH) (1) and Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10}) (2), have been synthesized successfully with the use of hydrothermal reactions. The crystal structures of the two compounds were determined by single-crystal X-ray diffraction. Compound 1 crystallizes in the polar space group Pca2{sub 1} (No. 29) while compound 2 crystallizes in the centrosymmetric space group C2/c (No. 15). The topography of compound 1 reveals a two-dimensional, layered structure comprised of VO{sub 6} octahedral chains and TeO{sub 3}(OH) zig-zag chains. Compound 2, on the contrary, features a three-dimensional [V{sub 4}O{sub 8}(Te{sub 3}O{sub 10})]{sup 4-} anionic framework withmore » Ba{sup 2+} ions filled into the 10-member ring helical tunnels. The [V{sub 4}O{sub 8}(Te{sub 3}O{sub 10})]{sup 4-} anionic network is the first 3D vanadium tellurite framework to be discovered in the alkaline-earth vanadium tellurite system. Powder second harmonic generation (SHG) measurements indicate that compound 1 shows a weak SHG response of about 0.3×KDP (KH{sub 2}PO{sub 4}) under 1064 nm laser radiation. Infrared spectroscopy, elemental analysis, thermal analysis, and dipole moment calculations have also been carried out. - Graphical abstract: VTeO{sub 4}(OH) (1) crystallizes in the noncentrosymmetric space group Pca2{sub 1} (No. 29) while Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10}) (2) crystallizes in the centrosymmetric space group C2/c (No. 15). - Highlights: • VTeO{sub 4}(OH) (1) and Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10}) (2) have been synthesized successfully with the use of hydrothermal reactions. • VTeO{sub 4}(OH) (1) crystallizes in the noncentrosymmetric space group Pca2{sub 1} and displays a weak SHG response. • VTeO{sub 4}(OH) (1) represents only the fourth SHG-active material found in vanadium tellurite systems. • Ba{sub 2}V{sub 4}O{sub 8}(Te{sub 3}O{sub 10}) (2) exhibits a novel three-dimensional [V{sub 4}O{sub 8}(Te{sub 3}O{sub 10})]{sup 4-} anionic framework.« less

Hydrothermal synthesis and characterization of a two-dimensional piperazinium cobalt–zinc phosphate via a metastable one-dimensional phase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Torre-Fernández, Laura; Khainakova, Olena A.; Espina, Aránzazu

2015-05-15

A two-dimensional piperazinium cobalt–zinc phosphate, formulated as (C{sub 4}N{sub 2}H{sub 12}){sub 1.5}(Co{sub 0.6}Zn{sub 0.4}){sub 2}(HPO{sub 4}){sub 2}(PO{sub 4})·H{sub 2}O (2D), was synthesized under hydrothermal conditions. The crystal structure was determined using single-crystal X-ray diffraction data (monoclinic P2{sub 1}/c, a=8.1165(3) Å, b=26.2301(10) Å, c=8.3595(4) Å, and β=110.930(5)°) and the hydrogen atom positions were optimized by DFT calculations. A single-crystal corresponding to one-dimensional metastable phase, (C{sub 4}N{sub 2}H{sub 12})Co{sub 0.3}Zn{sub 0.7}(HPO{sub 4}){sub 2}·H{sub 2}O (1D), was also isolated and the crystal structure was determined (monoclinic P2{sub 1}/c, a=8.9120(6) Å, b=14.0290(1) Å, c=12.2494(5) Å, and β=130.884(6)°). The bulk was characterized by chemical (C–H–N)more » analysis, powder X-ray diffraction (PXRD), powder X-ray thermodiffractometry (HT-XRD), transmission electron microscopy (STEM(DF)-EDX and EFTEM), and thermal analysis (TG/SDTA-MS), including activation energy data of its thermal decomposition. The magnetic susceptibility and magnetization measurements show no magnetic ordering down to 4 K. - Graphical abstract: Hydrothermal synthesis and structural characterization of a two-dimensional piperazinium cobalt–zinc phosphate, (C{sub 4}N{sub 2}H{sub 12}){sub 1.5}(Co{sub 0.6}Zn{sub 0.4}){sub 2}(HPO{sub 4}){sub 2}(PO{sub 4})·H{sub 2}O (2D), have been reported. The crystal structure of a one-dimensional piperazinium cobalt–zinc phosphate, (C{sub 4}N{sub 2}H{sub 12})Co{sub 0.3}Zn{sub 0.7}(HPO{sub 4}){sub 2}·H{sub 2}O (1D) a metastable phase during the hydrothermal synthesis, was also determined. The thermal behavior of 2D compound is strongly dependent on the selected heating rate and the magnetic susceptibility and magnetization measurements show no magnetic ordering down to 4 K. - Highlights: • A 2D piperazinium cobalt–zinc phosphate has been synthesized and characterized. • Crystal structure of 1D metastable phase was also determined. • Thermal behavior of 2D compound is strongly dependent on the selected heating rate. • Magnetic measurements show no magnetic ordering down to 4 K.« less

Crystallographic analysis of NHERF1–PLCβ3 interaction provides structural basis for CXCR2 signaling in pancreatic cancer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Yuanyuan; Wang, Shuo; Holcomb, Joshua

2014-04-04

Highlights: • CXCR2–NHERF1–PLCβ3 complex regulates CXCR2 signaling in pancreatic cancer. • The crystal structure of the NHERF1 PDZ1 domain in complex with PLCβ3. • The structure reveals specificity determinants of PDZ1–PLCβ3 interaction. • Endogenous PLCβ3 in pancreatic cancer cells interacts with both PDZ1 and PDZ2. • Structural basis of the PDZ1–PLCβ3 interaction is valuable in selective drug design. - Abstract: The formation of CXCR2–NHERF1–PLCβ3 macromolecular complex in pancreatic cancer cells regulates CXCR2 signaling activity and plays an important role in tumor proliferation and invasion. We previously have shown that disruption of the NHERF1-mediated CXCR2–PLCβ3 interaction abolishes the CXCR2 signaling cascademore » and inhibits pancreatic tumor growth in vitro and in vivo. Here we report the crystal structure of the NHERF1 PDZ1 domain in complex with the C-terminal PLCβ3 sequence. The structure reveals that the PDZ1–PLCβ3 binding specificity is achieved by numerous hydrogen bonds and hydrophobic contacts with the last four PLCβ3 residues contributing to specific interactions. We also show that PLCβ3 can bind both NHERF1 PDZ1 and PDZ2 in pancreatic cancer cells, consistent with the observation that the peptide binding pockets of these PDZ domains are highly structurally conserved. This study provides an understanding of the structural basis for the PDZ-mediated NHERF1–PLCβ3 interaction that could prove valuable in selective drug design against CXCR2-related cancers.« less

Solvent induced synthesis, structure and properties of coordination polymers based on 5-hydroxyisophthalic acid as linker and 1,10-phenanthroline as auxiliary ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kariem, Mukaddus; Yawer, Mohd; Sheikh, Haq Nawaz, E-mail: hnsheikh@rediffmail.com

2015-11-15

Three new coordination polymers [Mn(hip)(phen) (H{sub 2}O)]{sub n} (1), [Co(hip)(phen) (H{sub 2}O)]{sub n} (2), and [Cd(hip) (phen) (H{sub 2}O)]{sub n} (3) (H{sub 2}hip=5-hydroxyisophthalic acid; phen=1,10-phenanthroline) have been synthesized by solvo-hydrothermal method using diethyl formamide-water (DEF-H{sub 2}O) as solvent system. Single-crystal X-ray diffraction analysis reveals that all three coordination polymers 1, 2 and 3 crystallize in monoclinic space group P2/n. Metal ions are inter-connected by hydroxyisophthalate anions forming zig-zag 1D chain. 1D chains are further inter-connected by hydrogen bonding and π–π stacking interactions leading to 3D supramolecular architecture. Hydrogen-bonding and π–π stacking provide thermal stability to polymers. Compounds 1 and 2more » are paramagnetic at room temperature and variable temperature magnetic moment measurements revealed weak ferromagnetic interactions between metal ions at low temperature. Compound 3 exhibits excellent photoluminescence with large Stokes shift. - Graphical abstract: 1D helical chains of coordination polymers were synthesized by solvo-hydrothermal reaction of 5-hydroxyisopthalic acid and 1,10-phenanthroline with MnCl{sub 2}·4H{sub 2}O / CoCl{sub 2}·6H{sub 2}O / Cd(NO{sub 3}){sub 2}·6H{sub 2}O. - Highlights: • Solvent induced synthesis of three coordination polymers with 1D zig-zag structure. • Crystal structures of coordination polymers are reported and discussed. • 1,10-Phenanthroline influences magnetic and luminescent properties of polymers. • Coordination polymer of Cd is luminescent exhibiting large Stokes shift.« less

“Ni{sub 5}TiO{sub 7}” is Ni{sub 5}TiO{sub 4}(BO{sub 3}){sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nalbandyan, V.B.

2017-05-15

It is shown that the compound known as Ni{sub 5}TiO{sub 7} and considered as a promising catalyst and oxidation product of alloys does not exist and its XRD pattern actually corresponds to Ni{sub 5}TiO{sub 4}(BO{sub 3}){sub 2} - Graphical abstract: XRD pattern of “Ni{sub 5}TiO{sub 7}” (top) is identical to that for Ni{sub 5}TiO{sub 4}(BO{sub 3}){sub 2} (bottom) based on single-crystal structural data. - Highlights: • Popular catalyst known as Ni{sub 5}TiO{sub 7} is actually Ni{sub 5}TiO{sub 4}(BO{sub 3}){sub 2}. • B{sub 2}O{sub 3} came from the flux used for crystal growth. • Some authors reporting this phase did notmore » use any boron compounds.« less

The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals

PubMed Central

Freeman, Colin L.; Gong, Xiuqing; Levenstein, Mark A.; Wang, Yunwei; Kulak, Alexander; Anduix‐Canto, Clara; Lee, Phillip A.; Li, Shunbo; Chen, Li; Christenson, Hugo K.

2017-01-01

Abstract As crystallization processes are often rapid, it can be difficult to monitor their growth mechanisms. In this study, we made use of the fact that crystallization proceeds more slowly in small volumes than in bulk solution to investigate the effects of the soluble additives Mg2+ and poly(styrene sulfonate) (PSS) on the early stages of growth of calcite crystals. Using a “Crystal Hotel” microfluidic device to provide well‐defined, nanoliter volumes, we observed that calcite crystals form via an amorphous precursor phase. Surprisingly, the first calcite crystals formed are perfect rhombohedra, and the soluble additives have no influence on the morphology until the crystals reach sizes of 0.1–0.5 μm for Mg2+ and 1–2 μm for PSS. The crystals then continue to grow to develop morphologies characteristic of these additives. These results can be rationalized by considering additive binding to kink sites, which is consistent with crystal growth by a classical mechanism. PMID:28767197

Flow-induced crystallization in isotactic polypropylene

NASA Astrophysics Data System (ADS)

Hamad, Fawzi Ghassan

Brief intervals of strong flow stretch chains in a semicrystalline polymer melt, which results in an increase in the nuclei number density and a transformation of the crystal structure. This flow-induced crystallization (FIC) phenomenon is explored in this study using highly isotactic polypropylene (iPP) samples. Using one synthesized and five commercial linear isotactic polypropylene samples, we investigate the FIC behavior by imposing shear onto these samples in a rotational rheometer. Equipped with a good temperature control and flexible shear protocol, we apply different temperature and flow conditions. The magnitude of the FIC effect varies with basic processing parameters (shear rate, specific work, crystallization temperature, and shearing temperature) and material properties (totalistic, molecular weight distribution, and particle concentration in the polymer). The scope of this study is to systematically investigate the influences of these parameters on FIC. The FIC effects that are investigated in this dissertation are: crystallization kinetics, persistence time of flow-induced nuclei, and crystal morphology. The crystallization time was measured in the rheometer by monitoring the onset of crystallization after quenching samples sheared above Tm. These samples were subsequently used to study their flow-induced nuclei persistence time and crystal morphology. The lifetime of flow-induced nuclei was determined by measuring the time required to return from FIC back to quiescent crystallization using a differential scanning calorimeter. The crystal morphology was imaged using polarized optical microscopy and atomic force microscopy. We investigated the influence of specific work on the three FIC characteristics, and found three regimes that are separated by the critical work ( Wc) and the saturation work (Wsat) thresholds. Below the critical work threshold, the morphology is composed of mostly spherulite crystals, which keep a constant volume, and a small fraction of rice grain (anisotropic) crystals. The number of rice grain crystals increases with specific work, speeding up the crystallization time of the semicrystalline polymer. At critical work, spherulite formation stops, and the morphology consists only of rice grain structures. This morphology allows the sample to crystallize at higher temperatures when cooling at 5 C/min, with the sheared sample crystallizing at 129C compared to the unsheared sample at 113C. . Shearing isotactic polypropylene at higher temperatures reduced the FIC effect after subsequent quenching. Generally speaking, shearing at higher temperatures results in slower crystallization, but surprisingly, the influence of temperature is rather weak. Flow-induced crystallization persists even when shear is applied well above the equilibrium melting temperature (187C), finally weakening above the Hoffman-Weeks temperature (210C). This is likely due to the long lifetime of flow- induced precursors (crystallize to form rice grains), which remain stable at temperatures below 210C and only start to disappear slowly in prolonged annealing at temperatures above 210C (diminishing the FIC effect). Tacticity was found to govern the maximum nuclei number density in sheared samples; samples with lower isotactic content show a stronger FIC effect. Similarly, it was found that the concentration of particulates (mainly catalyst residue) are crucially important to FIC, samples with lower amounts of particles lowering the FIC nuclei number density. Data shows that the rate at which the crystallization time changes correlates with the prominence of the high molecular weight tail. A sample with a higher molecular weight tail in its distribution exhibits a faster change in crystallization time as a function of specific work. Similarly, increasing the molecular weight of the added component in a blend induces a larger change in the FIC behavior. (Abstract shortened by ProQuest.).

Revisiting the blind tests in crystal structure prediction: accurate energy ranking of molecular crystals.

PubMed

Asmadi, Aldi; Neumann, Marcus A; Kendrick, John; Girard, Pascale; Perrin, Marc-Antoine; Leusen, Frank J J

2009-12-24

In the 2007 blind test of crystal structure prediction hosted by the Cambridge Crystallographic Data Centre (CCDC), a hybrid DFT/MM method correctly ranked each of the four experimental structures as having the lowest lattice energy of all the crystal structures predicted for each molecule. The work presented here further validates this hybrid method by optimizing the crystal structures (experimental and submitted) of the first three CCDC blind tests held in 1999, 2001, and 2004. Except for the crystal structures of compound IX, all structures were reminimized and ranked according to their lattice energies. The hybrid method computes the lattice energy of a crystal structure as the sum of the DFT total energy and a van der Waals (dispersion) energy correction. Considering all four blind tests, the crystal structure with the lowest lattice energy corresponds to the experimentally observed structure for 12 out of 14 molecules. Moreover, good geometrical agreement is observed between the structures determined by the hybrid method and those measured experimentally. In comparison with the correct submissions made by the blind test participants, all hybrid optimized crystal structures (apart from compound II) have the smallest calculated root mean squared deviations from the experimentally observed structures. It is predicted that a new polymorph of compound V exists under pressure.

One-dimensional mercury(II) halide coordination polymers of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine ligand: Synthesis, crystal structure, spectroscopic and DFT studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saghatforoush, Lotfali, E-mail: saghatforoush@gmail.com; Khoshtarkib, Zeinab; Amani, Vahid

2016-01-15

Three new coordination polymers, [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl (1), Br (2)) and [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} (3) (bptz=3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) were synthesized. X-ray structural analysis indicated that compounds 1 and 2 are composed of one-dimensional (1D) linear chains while the compound 3 has 1D stair-stepped structure. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that compound 1 and 2 are direct band gap semiconductors; however, compound 3 is an indirect semiconductor. The linear optical properties of the compounds are also calculated by DFT method. According to the DFT calculations, the observed emission bandmore » of the compounds in solid state is due to electron transfer from an excited bptz-π* state (CBs) to the top of VBs. {sup 1}H NMR spectra of the compounds indicate that, in solution phase, the compounds don’t decompose completely. Thermal stability of the compounds is studied using TG, DTA methods. - Graphical abstract: Synthesis, crystal structure and emission spectra of [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl and Br) and [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} are presented. The electronic band structure and linear optical properties of the compounds are calculated by the DFT method. - Highlights: • Three 1D Hg(II) halide coordination polymers with bptz ligand have been prepared. • The structures of the compounds are determined by single crystal XRD. • DFT calculations show that [Hg(μ-bptz)X{sub 2}]{sub n} (X=Cl and Br) have a direct band gap. • DFT calculations show that [Hg{sub 2}(μ-bptz)(μ-I){sub 2}I{sub 2}]{sub n} has an indirect band gap. • The compounds show an intraligand electron transfer emission band in solid state.« less

Structural insights of the MLF1/14-3-3 interaction.

PubMed

Molzan, Manuela; Weyand, Michael; Rose, Rolf; Ottmann, Christian

2012-02-01

Myeloid leukaemia factor 1 (MLF1) binds to 14-3-3 adapter proteins by a sequence surrounding Ser34 with the functional consequences of this interaction largely unknown. We present here the high-resolution crystal structure of this binding motif [MLF1(29-42)pSer34] in complex with 14-3-3ε and analyse the interaction with isothermal titration calorimetry. Fragment-based ligand discovery employing crystals of the binary 14-3-3ε/MLF1(29-42)pSer34 complex was used to identify a molecule that binds to the interface rim of the two proteins, potentially representing the starting point for the development of a small molecule that stabilizes the MLF1/14-3-3 protein-protein interaction. Such a compound might be used as a chemical biology tool to further analyse the 14-3-3/MLF1 interaction without the use of genetic methods. Database Structural data are available in the Protein Data Bank under the accession number(s) 3UAL [14-3-3ε/MLF1(29-42)pSer34 complex] and 3UBW [14-3-3ε/MLF1(29-42)pSer34/3-pyrrolidinol complex] Structured digital abstract •  14-3-3 epsilon and MLF1 bind by x-ray crystallography (View interaction) •  14-3-3 epsilon and MLF1 bind by isothermal titration calorimetry (View Interaction: 1, 2). © 2011 The Authors Journal compilation © 2011 FEBS.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deus, R.C.; Cortés, J.A., E-mail: leandrosrr89@gmail.com; Ramirez, M.A.

Highlights: • CeO{sub 2} nanoparticles were obtained by microwave-hydrothermal method. • Rietveld refinement reveals a cubic structure. • KOH mineralizer agent exhibit weak agglomeration at low temperature and shorter time. - Abstract: The structural and photoluminescent properties at room temperature of CeO{sub 2} and La-doped CeO{sub 2} particles were undertaken. The obtained particles were synthesized by a microwave-assisted hydrothermal method (MAH) under different lanthanum contents. X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman), Ultra-violet spectroscopy (UV–vis) and photoluminescence (PL) measurements were carried out. XRD revealed that the powders are free of secondary phases and crystallize in themore » cubic structure. Raman data show that increasing La doping content increase oxygen vacancies due to lattice expansion. The UV/vis absorption spectroscopy suggested the presence of intermediate energy levels in the band gap of structurally ordered powders. Lanthanum addition creates oxygen vacancies and shifts the photoluminescence in the low energy range leading to intense PL emission.« less

Structure of Se-Te glasses studied using neutron, X-ray diffraction and reverse Monte Carlo modelling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Itoh, Keiji, E-mail: itoh@okayama-u.ac.jp; Research Reactor Institute, Kyoto University, Kumatori, Osaka 590-0494

Pulsed neutron diffraction and synchrotron X-ray diffraction measurements were performed on Se{sub 100-x}Te{sub x} bulk glasses with x=10, 20, 30 and 40. The coordination numbers obtained from the diffraction results demonstrate that Se and Te atoms are twofold coordinated and the glass structure is formed by the chain network. The three-dimensional structure model for Se{sub 60}Te{sub 40} glass obtained by using reverse Monte Carlo modelling shows that the alternating arrangements of Se and Te atoms compose the major part of the chain clusters but several other fragments such as Se{sub n} chains and Te-Te dimers are also present in largemore » numbers. The chain clusters have geometrically disordered forms and the interchain atomic order is different from those in the crystal structures of trigonal Se and trigonal Te. - Graphical abstract: Coordination environment in Se{sub 60}Te{sub 40} glass.« less

Base pairing and structural insights into the 5-formylcytosine in RNA duplex

PubMed Central

Wang, Rui; Luo, Zhipu; He, Kaizhang; Delaney, Michael O.; Chen, Doris; Sheng, Jia

2016-01-01

Abstract 5-Formylcytidine (f5C), a previously discovered natural nucleotide in the mitochondrial tRNA of many species including human, has been recently detected as the oxidative product of 5-methylcytidine (m5C) through 5-hydroxymethylcytidine (hm5C) in total RNA of mammalian cells. The discovery indicated that these cytosine derivatives in RNA might also play important epigenetic roles similar as in DNA, which has been intensively investigated in the past few years. In this paper, we studied the base pairing specificity of f5C in different RNA duplex contexts. We found that the 5-formyl group could increase duplex thermal stability and enhance base pairing specificity. We present three high-resolution crystal structures of an octamer RNA duplex [5′-GUA(f5C)GUAC-3′]2 that have been solved under three crystallization conditions with different buffers and pH values. Our results showed that the 5-formyl group is located in the same plane as the cytosine base and forms an intra-residue hydrogen bond with the amino group in the N4 position. In addition, this modification increases the base stacking between the f5C and the neighboring bases while not causing significant global and local structure perturbations. This work provides insights into the effects of 5-formylcytosine on RNA duplex. PMID:27079978

Viral genome packaging terminase cleaves DNA using the canonical RuvC-like two-metal catalysis mechanism

PubMed Central

Xu, Rui-Gang; Jenkins, Huw T.; Chechik, Maria; Blagova, Elena V.; Lopatina, Anna; Klimuk, Evgeny; Minakhin, Leonid; Severinov, Konstantin

2017-01-01

Abstract Bacteriophages and large dsDNA viruses encode sophisticated machinery to translocate their DNA into a preformed empty capsid. An essential part of this machine, the large terminase protein, processes viral DNA into constituent units utilizing its nuclease activity. Crystal structures of the large terminase nuclease from the thermophilic bacteriophage G20c show that it is most similar to the RuvC family of the RNase H-like endonucleases. Like RuvC proteins, the nuclease requires either Mn2+, Mg2+ or Co2+ ions for activity, but is inactive with Zn2+ and Ca2+. High resolution crystal structures of complexes with different metals reveal that in the absence of DNA, only one catalytic metal ion is accommodated in the active site. Binding of the second metal ion may be facilitated by conformational variability, which enables the two catalytic aspartic acids to be brought closer to each other. Structural comparison indicates that in common with the RuvC family, the location of the two catalytic metals differs from other members of the RNase H family. In contrast to a recently proposed mechanism, the available data do not support binding of the two metals at an ultra-short interatomic distance. Thus we postulate that viral terminases cleave DNA by the canonical RuvC-like mechanism. PMID:28100693

Structural determination of importin alpha in complex with beak and feather disease virus capsid nuclear localization signal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patterson, Edward I.; EH Graham Centre for Agricultural Innovation; Dombrovski, Andrew K.

2013-09-06

Highlights: •Circovirus capsid proteins contain large nuclear localization signals (NLS). •A method of nuclear import has not been elucidated. •Beak and feather disease virus (BFDV) capsid NLS was crystallized with importin α. •The structure showed BFDV NLS binding to the major site of importin α. •Result shows implications for mechanism of nuclear transport for all circoviruses. -- Abstract: Circoviruses represent a rapidly increasing genus of viruses that infect a variety of vertebrates. Replication requires shuttling viral molecules into the host cell nucleus, a process facilitated by capsid-associated protein (Cap). Whilst a nuclear localization signal (NLS) has been shown to mediatemore » nuclear translocation, the mode of nuclear transport remains to be elucidated. To better understand this process, beak and feather disease virus (BFDV) Cap NLS was crystallized with nuclear import receptor importin-α (Impα). Diffraction yielded structural data to 2.9 Å resolution, and the binding site on both Impα and BFDV Cap NLS were well resolved. The binding mechanism for the major site is likely conserved across circoviruses as supported by the similarity of NLSs in circovirus Caps. This finding illuminates a crucial step for infection of host cells by this viral family, and provides a platform for rational drug design against the binding interface.« less

Re-addressable Interconnects with Light-Induced Waveguides in Liquid Crystals

DTIC Science & Technology

2011-08-09

average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data...15. SUBJECT TERMS EOARD, Liquid Crystals, Laser beam control 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT...external stimuli, their performance is far from optimal: their response time can be larger than 100ms and they exhibit transverse fluctuations due

Synthesis, crystal structure, and properties of KSbO{sub 3}-type Bi{sub 3}Mn{sub 1.9}Te{sub 1.1}O{sub 11}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Manrong; Retuerto, Maria; Bok Go, Yong

2013-01-15

Single crystals of Bi{sub 3}Mn{sub 1.9}Te{sub 1.1}O{sub 11} were prepared from NaCl+KCl flux. This compound adopts KSbO{sub 3}-type crystal structure as evidenced by electron and single crystal X-ray diffraction analysis. The three-dimensional channel structure is formed by corner-sharing octahedral (Mn{sub 0.63}Te{sub 0.37}){sub 2}O{sub 10} dimers and two identical (Bi1){sub 4}(Bi2){sub 2} interpenetrating lattices. The intra-dimer Mn/Te-Mn/Te distances in Bi{sub 3}Mn{sub 1.9}Te{sub 1.1}O{sub 11} are short and are consistent with weak metal-metal interactions. The mixed oxidation state of manganese and the edge-sharing octahedral features are confirmed by X-ray near edge absorption spectroscopy measurements, which indicate Bi{sub 3}(Mn{sup III}{sub 1.1}Mn{sup IV}{sub 0.8})Te{supmore » VI}{sub 1.1}O{sub 11} with 57.7% Mn{sup 3+} and 42.3% Mn{sup 4+}. The partial substitution of Te for Mn perturbs long-range magnetic interactions, thereby destroying the ferromagnetic ordering found in Bi{sub 3}Mn{sub 3}O{sub 11} (T{sub C}=150 K). - Graphical abstract: Single crystal of Bi{sub 3}Mn{sub 1.9}Te{sub 1.1}O{sub 11} was grown from NaCl+KCl binary flux, suggesting that the high pressure Bi{sub 3}Mn{sub 3}O{sub 11} phase can be stabilized by partial substitution of Mn by Te at ambient pressure. Bi{sub 3}Mn{sub 1.9}Te{sub 1.1}O{sub 11} adopts a typical three dimensional KSbO{sub 3}-type crystal structure with three interpenetrating lattices and weak intra-dimmer metal-metal interaction caused by the d electrons of Mn. The edge-shared (Mn{sub 0.63}Te{sub 0.37}){sub 2}O{sub 10} octahedral dimer and mixed oxidation state of manganese (Bi{sub 3}(Mn{sup III}{sub 1.1}Mn{sup IV}{sub 0.8})Te{sup VI}{sub 1.1}O{sub 11} with 57.7% Mn{sup 3+} and 42.3% Mn{sup 4+}) features were evidenced by X-ray absorption near edge spectroscopy. Compared with Bi{sub 3}Mn{sub 3}O{sub 11}, the Te substituted Bi{sub 3}Mn{sub 1.9}Te{sub 1.1}O{sub 11} relaxes the crystal structure, but destroys the long-range magnetic ordering and gives short-range magnetic ordering below 5 K. Highlights: Black-Right-Pointing-Pointer High pressure Bi{sub 3}Mn{sub 3}O{sub 11} is stabilized by partial Te substitution at ambient pressure. Black-Right-Pointing-Pointer New KSbO{sub 3}-type Bi{sub 3}Mn{sub 1.9}Te{sub 1.1}O{sub 11} single crystal was grown from binary flux. Black-Right-Pointing-Pointer The presence of mixed oxidation state of manganese is evidenced by XANES study. Black-Right-Pointing-Pointer The Te-substitution destroys the long-range magnetic ordering and relaxes the structure.« less

Biosynthesis of amorphous mesoporous aluminophosphates using yeast cells as templates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sifontes, Ángela B., E-mail: asifonte@ivic.gob.ve; González, Gema; Tovar, Leidy M.

2013-02-15

Graphical abstract: Display Omitted Highlights: ► Amorphous aluminophosphates can take place using yeast as template. ► A mesoporous material was obtained. ► The specific surface area after calcinations ranged between 176 and 214 m{sup 2} g{sup −1}. -- Abstract: In this study aluminophosphates have been synthesized from aluminum isopropoxide and phosphoric acid solutions using yeast cells as template. The physicochemical characterization was carried out by thermogravimetric analysis; X-ray diffraction; Fourier transform infrared; N{sub 2} adsorption–desorption isotherms; scanning electron microscopy; transmission electron microscopy and potentiometric titration with N-butylamine for determination of: thermal stability; crystalline structure; textural properties; morphology and surface acidity,more » respectively. The calcined powders consisted of an intimate mixture of amorphous and crystallized AlPO particles with sizes between 23 and 30 nm. The average pore size observed is 13–16 nm and the specific surface area after calcinations (at 650 °C) ranged between 176 and 214 m{sup 2} g{sup −1}.« less

Syntheses, crystal structure, and electronic properties of the five ABaMQ{sub 4} compounds RbBaPS{sub 4}, CsBaPS{sub 4}, CsBaVS{sub 4}, RbBaVSe{sub 4}, and CsBaVSe{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mesbah, Adel; ICSM, UMR 5257 CEA / CNRS / UM / ENSCM, Site de Marcoule-Bâtiment 426, BP 17171, 30207 Bagnols-sur-Cèze Cedex; Prakash, Jai

Five new compounds belonging to the ABaMQ{sub 4} family were synthesized by solid-state chemistry at 1123 K. The compounds RbBaPS{sub 4}, CsBaPS{sub 4}, CsBaVS{sub 4}, RbBaVSe{sub 4}, and CsBaVSe{sub 4} are isostructural and have the TlEuPS{sub 4} structure type. They crystallize in space group D{sup 16}{sub 2h} – Pnma of the orthorhombic system. Their structure consists isolated MQ{sub 4} tetrahedra separated by A and Ba atoms to form a salt-like structure. Density Functional Theory (DFT) calculations of the electronic structures with the use of the HSE functional suggest that the compounds are semiconductors with calculated band gaps of 3.3 eVmore » (RbBaPS{sub 4}), 3.4 eV (CsBaPS{sub 4}), 2.3 eV (CsBaVS{sub 4}), and 1.6 eV (RbBaVSe{sub 4}). - Graphical abstract: General view of the ABaMQ{sub 4} structure down the a axis. - Highlights: • Five new ABaMQ{sub 4} compounds were synthesized by solid-state chemistry at 1123 K. • RbBaPS{sub 4}, CsBaPS{sub 4}, CsBaVS{sub 4}, RbBaVSe{sub 4}, and CsBaVSe{sub 4} have the TlEuPS{sub 4} structure type. • The compounds are semiconductors with calculated band gaps ranging from 1.6 to 3.4 eV.« less

The Li–Si–(O)–N system revisited: Structural characterization of Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Casas-Cabanas, M.; Santner, H.; Palacín, M.R., E-mail: rosa.palacin@icmab.es

2014-05-01

A systematic study of the Li–Si–(O)–N system is presented. The synthetic conditions to prepare Li{sub 2}SiN{sub 2}, Li{sub 5}SiN{sub 3}, Li{sub 18}Si{sub 3}N{sub 10}, Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are described and the structure of the last two compounds has been solved for the first time. While Li{sub 21}Si{sub 3}N{sub 11} crystallizes as a superstructure of the anti-fluorite structure with Li and Si ordering, Li{sub 7}SiN{sub 3}O exhibits the anti-fluorite structure with both anion and cation disorder. - Graphical abstract: A systematic study of the Li–Si–(O)–N system is presented. Li{sub 21}Si{sub 3}N{sub 11} crystallizes as a superstructuremore » of the anti-fluorite structure with Li and Si ordering, Li{sub 7}SiN{sub 3}O exhibits the anti-fluorite structure with both anion and cation disorder. - Highlights: • Li{sub 2}SiN{sub 2}, Li{sub 5}SiN{sub 3}, Li{sub 18}Si{sub 3}N{sub 10}, Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are prepared. • The structures of Li{sub 21}Si{sub 3}N{sub 11} and Li{sub 7}SiN{sub 3}O are presented. • Li{sub 21}Si{sub 3}N{sub 11} exhibits an anti-fluorite superstructure with Li and Si ordering.« less

Crystal growth of Bi{sub 2}Te{sub 3} and noble cleaved (0001) surface properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Atuchin, V.V., E-mail: atuchin@thermo.isp.nsc.ru; Functional Electronics Laboratory, Tomsk State University, Tomsk 634050; Golyashov, V.A.

2016-04-15

A high quality Bi{sub 2}Te{sub 3} crystal has been grown by Bridgman method with the use of rotating heat field. The phase purity and bulk structural quality of the crystal have been verified by XRD analysis and rocking curve observation. The atomically smooth Bi{sub 2}Te{sub 3}(0001) surface with an excellent crystallographic quality is formed by cleavage in the air. The chemical and microstructural properties of the surface have been evaluated with RHEED, AFM, STM, SE and XPS. The Bi{sub 2}Te{sub 3}(0001) cleaved surface is formed by atomically smooth terraces with the height of the elemental step of ~1.04±0.1 nm, asmore » estimated by AFM. There is no surface oxidation process detected over a month keeping in the air at normal conditions, as shown by comparative core level photoelectron spectroscopy. - Graphical abstract: A high quality Bi{sub 2}Te{sub 3} crystal has been grown by Bridgman method with the use of rotating heat field and the Bi{sub 2}Te{sub 3}(0001) cleaved surface has been evaluated with RHEED, AFM, STM, SE and XPS. - Highlights: • High-quality Bi{sub 2}Te{sub 3} crystal of 10 mm in diameter and 50 mm long have been grown. • The high-purity cleaved Bi{sub 2}Te{sub 3}(0001) surface has been evaluated by RHEED, AFM, STM and XPS methods. • The Bi{sub 2}Te{sub 3} surface covered by atomically smooth (0001) terraces is chemically stable for a long time.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hossain, M. Anwar; Center for Crystal Science and Technology, University of Yamanashi, Miyamae 7-32, Kofu, Yamanashi 400-8511; Tanaka, Isao

We studied thermoelectric properties of YB{sub 41}Si{sub 1.3} single crystals grown by the floating zone method. The composition of the grown crystal was confirmed by electron probe micro-analysis. We have determined the growth direction for the first time for these borosilicides, and discovered relatively large anisotropy in electrical properties. We measured the electrical resistivity and Seebeck coefficient along [510] (the growth direction) and [052] directions and we found that this crystal exhibits strong electrical anisotropy with a maximum of more than 8 times. An interesting layered structural feature is revealed along [510] with dense boron cluster layers and yttrium layers,more » with conductivity enhanced along this direction. We obtained 3.6 times higher power factor along [510] compared to that along [052]. Although the ZT of the present system is low, anisotropy in the thermoelectric properties of a boride was reported for the first time, and can be a clue in developing other boride systems also. - Graphical abstract: The growth direction ([510]) was determined for the first time in YB{sub 41}Si{sub 1.3} single crystals and revealed an interesting layered feature of boron clusters and metal atoms, along which the electrical conductivity and thermoelectric power factor was strongly enhanced. - Highlights: • We have grown YB{sub 41}Si{sub 1.3} single crystals by the floating zone method. • Growth direction of [510] determined for first time in REB{sub 41}Si{sub 1.2}. • Electrical resistivity was strongly anisotropic with possible enhancement along metal layers. • The obtained power factor along [510] is 3.6 times higher than that along [052].« less

EBSD characterization of the growth mechanism of SiC synthesized via direct microwave heating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jigang, E-mail: wangjigang@seu.edu.cn; Xizang Key Laboratory of Optical Information Processing and Visualization Technology, School of Information Engineering, Xizang Minzu University, Xianyang 712082; Huang, Shan

2016-04-15

Well-crystallized 3C-silicon carbide (SiC) grains/nanowires have been synthesized rapidly and conveniently via direct microwave heating, simply using silicon dioxide powders and artificial graphite as raw materials. The comprehensive characterizations have been employed to investigate the micro-structure of the obtained 3C-SiC products. Results indicated that, different from the classic screw dislocation growth mechanism, the 3C-SiC grains/nanowires synthesized via high-energy vacuum microwave irradiation were achieved through the two-dimension nucleation and laminar growth mechanism. Especially, the electron backscattered diffraction (EBSD) was employed to characterize the crystal planes of the as-grown SiC products. The calculated Euler angles suggested that the fastest-growing crystal planes (211)more » were overlapped gradually. Through the formation of the (421) transformation plane, (211) finally evolved to (220) which existed as the side face of SiC grains. The most stable crystal planes (111) became the regular hexagonal planes in the end, which could be explained by the Bravais rule. The characterization results of EBSD provided important experimental information for the evolution of crystal planes. - Graphical abstract: The formation of 3C-SiC prepared via direct microwave heating follows the mechanism of two-dimension nucleation and laminar growth. - Highlights: • 3C−SiC grains/nanowires were obtained via direct microwave heating. • 3C−SiC followed the mechanism of two-dimension nucleation and laminar growth. • In-situ EBSD analysis provided the experimental evidences of the growth.« less

Crystal engineering of ibuprofen compounds: From molecule to crystal structure to morphology prediction by computational simulation and experimental study

NASA Astrophysics Data System (ADS)

Zhang, Min; Liang, Zuozhong; Wu, Fei; Chen, Jian-Feng; Xue, Chunyu; Zhao, Hong

2017-06-01

We selected the crystal structures of ibuprofen with seven common space groups (Cc, P21/c, P212121, P21, Pbca, Pna21, and Pbcn), which was generated from ibuprofen molecule by molecular simulation. The predicted crystal structures of ibuprofen with space group P21/c has the lowest total energy and the largest density, which is nearly indistinguishable with experimental result. In addition, the XRD patterns for predicted crystal structure are highly consistent with recrystallization from solvent of ibuprofen. That indicates that the simulation can accurately predict the crystal structure of ibuprofen from the molecule. Furthermore, based on this crystal structure, we predicted the crystal habit in vacuum using the attachment energy (AE) method and considered solvent effects in a systematic way using the modified attachment energy (MAE) model. The simulation can accurately construct a complete process from molecule to crystal structure to morphology prediction. Experimentally, we observed crystal morphologies in four different polarity solvents compounds (ethanol, acetonitrile, ethyl acetate, and toluene). We found that the aspect ratio decreases of crystal habits in this ibuprofen system were found to vary with increasing solvent relative polarity. Besides, the modified crystal morphologies are in good agreement with the observed experimental morphologies. Finally, this work may guide computer-aided design of the desirable crystal morphology.

Copper(II) complexes with 4-(1H-1, 2, 4-trizol-1-ylmethyl) benzoic acid: Syntheses, crystal structures and antifungal activities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiong, Pingping; Li, Jie; Bu, Huaiyu, E-mail: 7213792@qq.com

2014-07-01

Reaction of Cu(II) with an asymmetric semi-rigid organic ligand 4-(1H-1, 2, 4-trizol-1-ylmethyl) benzoic acid (HL), yielded five compounds, [Cu{sub 0.5}L]{sub n} (1), [Cu(HL){sub 2}Cl{sub 2}]{sub n} (2), [Cu(HL){sub 2}Cl{sub 2}(H{sub 2}O)] (3), [Cu(L){sub 2}(H{sub 2}O)]{sub n} (4) and [Cu(L)(phen)(HCO{sub 2})]{sub n} (5), which have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. As for compounds 1, 2 and 5, Cu(II) is bridged through HL, Cl{sup -}, and formic acid, respectively, featuring 1D chain-structure. In compound 3, Cu(II) with hexahedral coordination sphere is assembled through hydrogen-bonding into 3D supramolecular framework. In compound 4, 1D chain units –Cu–O–Cu–O–more » are ligand-bridged into a 3D network. All compounds were tested on fungi (Fusarium graminearum, Altemaria solani, Macrophoma kawatsukai, Alternaria alternata and Colletotrichum gloeosporioides). Compound 1 exhibits a better antifungal effect compared to other compounds. An effect of structure on the antifungal activity has also been correlated. - Graphical abstract: Copper(II) compounds with 4-(1H-1, 2, 4-trizol-1-ylmethyl) benzoic acid, were prepared, structurally characterized and investigated for antifungal activity. - Highlights: • The title compounds formed by thermodynamics and thermokinetics. • The five compounds show higher inhibition percentage than reactants. • The structure effect on the antifungal activity.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Yue; College of Life Science, Dalian Nationalities University, Dalian, Liaoning 116600; Chen, Baojiu, E-mail: chenmbj@sohu.com

Tb{sup 3+}, Eu{sup 3+} codoped YF{sub 3} nano- and micro-crystals with the morphologies of ellipsoid-like nanoplate, spindle, sandwich-structural rhombus and nanoaggregate were synthesized through a solvothermal method. The morphologies of the prepared products can be tailored by controlling the volume ratio of ethylene glycol (EG) to H{sub 2}O, solvent type or the reaction time. A possible formation mechanism of the sandwich-structural rhombus like YF{sub 3} phosphor was proposed. The emitting colors of YF{sub 3}:Tb{sup 3+},Eu{sup 3+} phosphors can be easily tuned from yellowish green, yellow to orange by increasing Eu{sup 3+} concentration. The energy transfer from Tb{sup 3+} to Eu{supmore » 3+} in YF{sub 3} phosphors was studied. It was found that the interaction type between Tb{sup 3+} and Eu{sup 3+} is electric dipole-dipole interaction. - Graphical abstract: Sandwich-structural rhombus like YF{sub 3}:Tb{sup 3+}, Eu{sup 3+} phosphors were synthesized through a solvothermal process. The formation mechanism of the sandwich-structural rhombus like YF{sub 3}:Tb{sup 3+}, Eu{sup 3+} phosphors was studied. Highlights: Black-Right-Pointing-Pointer YF{sub 3} nano- and micro-crystals were synthesized through solvothermal route. Black-Right-Pointing-Pointer A formation mechanism of the sandwich-structural rhombus like YF{sub 3} was proposed. Black-Right-Pointing-Pointer The emitting colors of YF{sub 3}:Tb{sup 3+},Eu{sup 3+} phosphors can be tuned. Black-Right-Pointing-Pointer Energy transfer from Tb{sup 3+} to Eu{sup 3+} is confirmed as electric dipole-dipole interaction.« less

Applications of the Cambridge Structural Database in organic chemistry and crystal chemistry.

PubMed

Allen, Frank H; Motherwell, W D Samuel

2002-06-01

The Cambridge Structural Database (CSD) and its associated software systems have formed the basis for more than 800 research applications in structural chemistry, crystallography and the life sciences. Relevant references, dating from the mid-1970s, and brief synopses of these papers are collected in a database, DBUse, which is freely available via the CCDC website. This database has been used to review research applications of the CSD in organic chemistry, including supramolecular applications, and in organic crystal chemistry. The review concentrates on applications that have been published since 1990 and covers a wide range of topics, including structure correlation, conformational analysis, hydrogen bonding and other intermolecular interactions, studies of crystal packing, extended structural motifs, crystal engineering and polymorphism, and crystal structure prediction. Applications of CSD information in studies of crystal structure precision, the determination of crystal structures from powder diffraction data, together with applications in chemical informatics, are also discussed.

Validation of experimental molecular crystal structures with dispersion-corrected density functional theory calculations.

PubMed

van de Streek, Jacco; Neumann, Marcus A

2010-10-01

This paper describes the validation of a dispersion-corrected density functional theory (d-DFT) method for the purpose of assessing the correctness of experimental organic crystal structures and enhancing the information content of purely experimental data. 241 experimental organic crystal structures from the August 2008 issue of Acta Cryst. Section E were energy-minimized in full, including unit-cell parameters. The differences between the experimental and the minimized crystal structures were subjected to statistical analysis. The r.m.s. Cartesian displacement excluding H atoms upon energy minimization with flexible unit-cell parameters is selected as a pertinent indicator of the correctness of a crystal structure. All 241 experimental crystal structures are reproduced very well: the average r.m.s. Cartesian displacement for the 241 crystal structures, including 16 disordered structures, is only 0.095 Å (0.084 Å for the 225 ordered structures). R.m.s. Cartesian displacements above 0.25 A either indicate incorrect experimental crystal structures or reveal interesting structural features such as exceptionally large temperature effects, incorrectly modelled disorder or symmetry breaking H atoms. After validation, the method is applied to nine examples that are known to be ambiguous or subtly incorrect.

Geometric magnetic frustration in RE{sub 2}O{sub 2}S oxysulfides (RE = Sm, Eu and Gd)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Biondo, V.; Sarvezuk, P.W.C.; Ivashita, F.F.

2014-06-01

Graphical abstract: Stacked planes in the <001> direction of an oxysulfide structure, showing the triangular nets formed by rare earth cations, which moments present geometric magnetic frustration. - Highlights: • We prepared monophasic RE{sub 2}O{sub 2}S Oxysulfides (RE = Sm, Eu and Gd). • RE{sub 2}O{sub 2}S compounds were characterized regarding structural and magnetic properties. • Mössbauer spectra were obtained for Eu{sub 2}O{sub 2}S and Gd{sub 2}O{sub 2}S at different temperatures. • Oxysulfides present geometric magnetic frustration of the rare-earth sublattice. - Abstract: RE{sub 2}O{sub 2}S oxysulfides (with RE = Sm, Eu and Gd) were prepared and characterized regarding theirmore » structural and magnetic properties. The compounds crystallized in the trigonal symmetry (space group P-3m/D{sub 3}{sup 3}d), with the lattice parameter varying linearly with the ionic radius of the RE cation. All these oxysulfides are magnetically frustrated and only the gadolinium sample showed magnetic order down to 3 K. The magnetic frustration is attributed to the spatial distribution of cations over the lattice, where the RE’s magnetic moments occupy the sites forming a triangular plane lattice, perpendicular to the direction. This geometric magnetic frustration was firstly recognized for these oxysulfides.« less

Heterobimetallic thiocyanato-bridged coordination polymers based on [Hg(SCN){sub 4}]{sup 2-}: Synthesis, crystal structure, magnetic properties and ESR studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jian Fangfang; Xiao Hailian; Liu Faqian

2006-12-15

Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN){sub 4}Ni(Im){sub 3}] {sub {infinity}} 1, [Hg(SCN){sub 4}Mn(Im){sub 2}] {sub {infinity}} 2, and [Hg(SCN){sub 4}Cu(Me-Im){sub 2} Hg(SCN){sub 4}Cu(Me-Im){sub 4}] {sub {infinity}} 3, (Im=imidazole, Me-Im=N-methyl-imidazole), have been synthesized and characterized by means of elemental analysis, ESR, and single-crystal X-ray. X-ray diffraction analysis reveals that these three complexes all form 3D network structure, and their structures all contain a thiocyanato-bridged Hg...Hg chain (M=Mn, Ni, Cu) in which the metal and mercury centers exhibit different coordination environments. In complex 1, the [Hg(SCN){sub 4}]{sup 2-} anion connects three [Ni(Im){sub 3}]{sup 2+} using three SCN ligands giving risemore » to a 3D structure, and in complex 2, four SCN ligands bridge [Hg(SCN){sub 4}]{sup 2-} and [Mn(Im){sub 2}]{sup 2+} to form a 3D structure. The structure of 3 contains two copper atoms with distinct coordination environment; one is coordinated by four N-methyl-imidazole ligands and two axially elongated SCN groups, and another by four SCN groups (two elongated) and two N-methyl-imidazole ligands. The magnetic property of complex 1 has been investigated. The spin state structure in hetermetallic NiHgNi systems of complex 1 is irregular. The ESR spectra results of complex 3 demonstrate Cu{sup 2+} ion lie on octahedral environment. -- Graphical abstract: Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN){sub 4}Ni(Im){sub 3}] {sub {infinity}} 1, [Hg(SCN){sub 4}Mn(Im){sub 2}] {sub {infinity}} 2, and [Hg(SCN){sub 4}Cu(Me-Im){sub 2} Hg(SCN){sub 4}Cu(Me-Im){sub 4}] {sub {infinity}} 3, (Im=imidazole, Me-Im=N-methyl-imidazole), have been synthesized and characterized by single-crystal X-ray. All coordination polymers possess 3-D structures, and consist of organic base neutral ligands (imidazole and N-methyl-imidazole) and SCN{sup -1} anions. Their structural difference is maicaused by the role of the organic base and metal ions. The complex 1 shows the irregular spin state structure.« less

Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl: Interesting size effects originated from the tetrahedral anions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Ming-Yan; Xia, Sheng-Qing, E-mail: shqxia@sdu.edu.cn; Liu, Xiao-Cun

2014-11-15

Two new barium chalcogenides, Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl, were synthesized by using high temperature solid-state reactions and their structures were determined by single-crystal X-ray diffraction technique. Despite the similar chemical formula, the structures of Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl are subtly different due to the size effects originated from the tetrahedral anions. Ba{sub 3}GeS{sub 5} crystallizes in the orthorhombic space group Pnma (no. 62) with cell parameters of a=12.0528(9) Å, b=9.5497(7) Å and c=8.5979(6) Å, while Ba{sub 3}InS{sub 4}Cl adopts a different tetragonal system (space group: I4/mcm, no. 140, a=b=8.3613(6) Å, c=14.3806(18) Å). The measuredmore » optical band gap of Ba{sub 3}GeS{sub 5} is 3.0 eV, a little smaller than the value of 3.42 eV in Ba{sub 3}InS{sub 4}Cl. Theoretical calculations by Wien2k are provided as well in order to better understand these results. - Graphical abstract: The polyhedral structure view for Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl in which Ba, S and Cl atoms are plotted in purple, red and green spheres. - Highlights: • Two new barium chalcogenides, Ba{sub 3}GeS{sub 5} and Ba{sub 3}InS{sub 4}Cl, were synthesized from the BaCl{sub 2}-flux reactions. • Their crystal structures feature discrete [MS{sub 4}] tetrahedra which embody interesting size effects. • Both compounds exhibit a band gap around 3.0 eV. • They are thermally stable up to 1073 K.« less

A new family of metal borohydride guanidinate complexes: Synthesis, structures and hydrogen-storage properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Hui, E-mail: huiwu@nist.gov; Zhou, Xiuquan; Rodriguez, Efrain E.

We report on a new class of complex hydrides: borohydride guanidinate complexes (MBH{sub 4}·nCN{sub 3}H{sub 5}, M=Li, Mg, and Ca). They can be prepared via facile solid-state synthesis routes. Their crystal structures were successfully determined using a combination of X-ray diffraction, first-principles calculations and neutron vibrational spectroscopy. Among these compounds, Mg(BH{sub 4}){sub 2}·6CN{sub 3}H{sub 5} is composed of large complex Mg[CN{sub 3}H{sub 5}]{sub 6}{sup 2+} cations and surrounding BH{sub 4}{sup -} ions, while Ca(BH{sub 4}){sub 2}·2CN{sub 3}H{sub 5} possesses layers of corner-sharing Ca[BH{sub 4}]{sub 4}(CN{sub 3}H{sub 5}){sub 2} octahedra. Our dehydrogenation results show that ≈10 wt% hydrogen can be releasedmore » from MBH{sub 4}·nCN{sub 3}H{sub 5} (M=Li, Mg, and Ca) at moderate temperatures with minimal ammonia and diborane contamination thanks to the synergistic effect of C-N bonds from guanidine and hydridic H from borohydrides leading to a weakening of the N-H bonds, thus impeding ammonia gas liberation. Further tuning the dehydrogenation with different cation species indicates that Mg(BH{sub 4}){sub 2}·nCN{sub 3}H{sub 5} can exhibit the optimum properties with nearly thermally neutral dehydrogenation and very high purity hydrogen release. - Graphical abstract: A new family of complex hydrides: borohydride guanidinates, was developed with diverse crystal structures and remarkable hydrogen storage properties. - Highlights: • A new family of complex hydrides, borohydride guanidinate complexes, are synthesized. • Their diverse crystal structures are determined using combined characterizations. • These compounds can release ~10 wt% pure H{sub 2} at moderate temperatures. • Dehydrogenation thermodynamics and H{sub 2} purity can be tuned by varying cation species.« less

Crystal structure and magnetic properties of high-oxygen pressure annealed Sr{sub 1-x}La{sub x}Co{sub 0.5}Fe{sub 0.5}O{sub 3-{delta}} (0{<=}x{<=}0.5)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swierczek, Konrad; Materials Science Division, Argonne National Laboratory, Argonne, IL 60439; Dabrowski, Bogdan

2009-02-15

Structural and magnetic studies are presented for the perovskite type Sr{sub 1-x}La{sub x}Co{sub 0.5}Fe{sub 0.5}O{sub 3-{delta}} (0{<=}x{<=}0.5) materials annealed under moderately high-oxygen pressures of {approx}200 atm. A detailed analysis of the room temperature neutron time-of-flight diffraction data reveals that the crystal structure of the sample SrCo{sub 0.5}Fe{sub 0.5}O{sub 2.89(1)}, previously described as vacancy-disordered cubic, is similar to the formerly reported, oxygen-vacancy ordered Sr{sub 8}Fe{sub 8}O{sub 23} compound, i.e. Sr{sub 8}Co{sub 4}Fe{sub 4}O{sub 23} is tetragonal with the I4/mmm symmetry. With an increase of the La content the studied materials become nearly oxygen stoichiometric and a lowering of the crystal symmetrymore » is observed from cubic Pm3-barm (x=0.1 and 0.2) to tetragonal I4/mcm (x=0.3 and 0.4), and finally to monoclinic I12/c1 (x=0.5). Low-temperature structural and magnetic measurements show a ferromagnetic ordering with the maximum Curie temperature near 290 K at x=0.2. - Graphical Abstract: Room temperature Rietveld refinement profile using I4/mmm space group for the oxygen vacancy ordered SrCo{sub 0.5}Fe{sub 0.5}O{sub 2.89} (Sr{sub 8}Co{sub 4}Fe{sub 4}O{sub 23}). Top tick-marks denote allowed reflections in I4/mmm, bottom one emphasize the possibility of inexact indexing using Pm3-barm symmetry. Previous reports indicate that similar ordering is common for SrCo{sub 1-x}Fe{sub x}O{sub 3-{delta}} compounds possibly hindering their applications.« less

Five Fatty Aldehyde Dehydrogenase Enzymes from Marinobacter and Acinetobacter spp. and Structural Insights into the Aldehyde Binding Pocket

PubMed Central

Bertram, Jonathan H.; Mulliner, Kalene M.; Shi, Ke; Plunkett, Mary H.; Nixon, Peter; Serratore, Nicholas A.; Douglas, Christopher J.; Aihara, Hideki

2017-01-01

ABSTRACT Enzymes involved in lipid biosynthesis and metabolism play an important role in energy conversion and storage and in the function of structural components such as cell membranes. The fatty aldehyde dehydrogenase (FAldDH) plays a central function in the metabolism of lipid intermediates, oxidizing fatty aldehydes to the corresponding fatty acid and competing with pathways that would further reduce the fatty aldehydes to fatty alcohols or require the fatty aldehydes to produce alkanes. In this report, the genes for four putative FAldDH enzymes from Marinobacter aquaeolei VT8 and an additional enzyme from Acinetobacter baylyi were heterologously expressed in Escherichia coli and shown to display FAldDH activity. Five enzymes (Maqu_0438, Maqu_3316, Maqu_3410, Maqu_3572, and the enzyme reported under RefSeq accession no. WP_004927398) were found to act on aldehydes ranging from acetaldehyde to hexadecanal and also acted on the unsaturated long-chain palmitoleyl and oleyl aldehydes. A comparison of the specificities of these enzymes with various aldehydes is presented. Crystallization trials yielded diffraction-quality crystals of one particular FAldDH (Maqu_3316) from M. aquaeolei VT8. Crystals were independently treated with both the NAD+ cofactor and the aldehyde substrate decanal, revealing specific details of the likely substrate binding pocket for this class of enzymes. A likely model for how catalysis by the enzyme is accomplished is also provided. IMPORTANCE This study provides a comparison of multiple enzymes with the ability to oxidize fatty aldehydes to fatty acids and provides a likely picture of how the fatty aldehyde and NAD+ are bound to the enzyme to facilitate catalysis. Based on the information obtained from this structural analysis and comparisons of specificities for the five enzymes that were characterized, correlations to the potential roles played by specific residues within the structure may be drawn. PMID:28389542

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yahyaoui, Samia; Rekik, Walid; Laboratoire Sciences Chimiques de Rennes

The crystal structures of 1,4-diazabicyclo[2.2.2]octane (dabco)-templated iron sulfate, (C{sub 6}H{sub 14}N{sub 2})[Fe(H{sub 2}O){sub 6}](SO{sub 4}){sub 2}, were determined at room temperature and at -173 deg. C from single-crystal X-ray diffraction. At 20 deg. C, it crystallises in the monoclinic symmetry, centrosymmetric space group P2{sub 1}/n, Z=2, a=7.964(5), b=9.100(5), c=12.065(5) A, {beta}=95.426(5) deg. and V=870.5(8) A{sup 3}. The structure consists of [Fe(H{sub 2}O){sub 6}]{sup 2+} and disordered (C{sub 6}H{sub 14}N{sub 2}){sup 2+} cations and (SO{sub 4}){sup 2-} anions connected together by an extensive three-dimensional H-bond network. The title compound undergoes a reversible phase transition of the first-order at -2.3 deg. C,more » characterized by DSC, dielectric measurement and optical observations, that suggests a relaxor-ferroelectric behavior. Below the transition temperature, the compound crystallizes in the monoclinic system, non-centrosymmetric space group Cc, with eight times the volume of the ambient phase: a=15.883(3), b=36.409(7), c=13.747(3) A, {beta}=120.2304(8){sup o}, Z=16 and V=6868.7(2) A{sup 3}. The organic moiety is then fully ordered within a supramolecular structure. Thermodiffractometry and thermogravimetric analyses indicate that its decomposition proceeds through three stages giving rise to the iron oxide. - Graphical abstract: The new dabcodiium hexaaquairon(II) bis(sulfate), (C{sub 6}H{sub 14}N{sub 2})[Fe(H{sub 2}O){sub 6}](SO{sub 4}){sub 2}, was prepared and characterized. It exhibits a supramolecular structure and undergoes a reversible order-disorder phase transition at -2.3 deg. C.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kahlenberg, Volker; Konzett, Juergen; Kaindl, Reinhard

High-pressure synthesis experiments in the system Na{sub 2}O-Y{sub 2}O{sub 3}-SiO{sub 2} revealed the existence of a previously unknown polymorph of NaYSi{sub 2}O{sub 6} or Na{sub 3}Y{sub 3}[Si{sub 3}O{sub 9}]{sub 2} which was quenched from 3.0 GPa and 1000 deg. C. Structural investigations on this modification have been performed using single-crystal X-ray diffraction data collected at ambient conditions. Furthermore, unpolarized micro-Raman spectra have been obtained from single-crystal material. The high-P modification of NaYSi{sub 2}O{sub 6} crystallizes in the centrosymmetric space group C2/c with 12 formula units per cell (a=8.2131(9) A, b=10.3983(14) A, c=17.6542(21) A, {beta}=100.804(9){sup o}, V=1481.0(3) A{sup 3}, R(|F|)=0.033 formore » 1142 independent observed reflections) and belongs to the group of cyclo-silicates. Basic building units are isolated three-membered [Si{sub 3}O{sub 9}] rings located in layers parallel to (010). Within a single layer the rings are concentrated in strings parallel to [100]. The sequence of directedness of up (U) or down (D) pointing tetrahedra of a single ring is UUU or DDD, respectively. Stacking of the layers parallel to b results in the formation of a three-dimensional structure in which yttrium and sodium cations are incorporated for charge compensation. In more detail, four non-tetrahedral cation positions can be differentiated which are coordinated by 6 and 8 oxygen ligands. Refinements of the site occupancies did not reveal any indication for mixed Na-Y populations on these positions. Finally, several geometrical parameters of rings occurring in cyclo-trisilicate structures have been compiled and are discussed. - Graphical abstract: Projection of the whole structure of high-P NaYSi{sub 2}O{sub 6} parallel to [100].« less

Five Fatty Aldehyde Dehydrogenase Enzymes from Marinobacter and Acinetobacter spp. and Structural Insights into the Aldehyde Binding Pocket

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bertram, Jonathan H.; Mulliner, Kalene M.; Shi, Ke

ABSTRACT Enzymes involved in lipid biosynthesis and metabolism play an important role in energy conversion and storage and in the function of structural components such as cell membranes. The fatty aldehyde dehydrogenase (FAldDH) plays a central function in the metabolism of lipid intermediates, oxidizing fatty aldehydes to the corresponding fatty acid and competing with pathways that would further reduce the fatty aldehydes to fatty alcohols or require the fatty aldehydes to produce alkanes. In this report, the genes for four putative FAldDH enzymes fromMarinobacter aquaeoleiVT8 and an additional enzyme fromAcinetobacter baylyiwere heterologously expressed inEscherichia coliand shown to display FAldDH activity.more » Five enzymes (Maqu_0438, Maqu_3316, Maqu_3410, Maqu_3572, and the enzyme reported under RefSeq accession no.WP_004927398) were found to act on aldehydes ranging from acetaldehyde to hexadecanal and also acted on the unsaturated long-chain palmitoleyl and oleyl aldehydes. A comparison of the specificities of these enzymes with various aldehydes is presented. Crystallization trials yielded diffraction-quality crystals of one particular FAldDH (Maqu_3316) fromM. aquaeoleiVT8. Crystals were independently treated with both the NAD +cofactor and the aldehyde substrate decanal, revealing specific details of the likely substrate binding pocket for this class of enzymes. A likely model for how catalysis by the enzyme is accomplished is also provided. IMPORTANCEThis study provides a comparison of multiple enzymes with the ability to oxidize fatty aldehydes to fatty acids and provides a likely picture of how the fatty aldehyde and NAD +are bound to the enzyme to facilitate catalysis. Based on the information obtained from this structural analysis and comparisons of specificities for the five enzymes that were characterized, correlations to the potential roles played by specific residues within the structure may be drawn.« less

In-situ and real-time growth observation of high-quality protein crystals under quasi-microgravity on earth.

PubMed

Nakamura, Akira; Ohtsuka, Jun; Kashiwagi, Tatsuki; Numoto, Nobutaka; Hirota, Noriyuki; Ode, Takahiro; Okada, Hidehiko; Nagata, Koji; Kiyohara, Motosuke; Suzuki, Ei-Ichiro; Kita, Akiko; Wada, Hitoshi; Tanokura, Masaru

2016-02-26

Precise protein structure determination provides significant information on life science research, although high-quality crystals are not easily obtained. We developed a system for producing high-quality protein crystals with high throughput. Using this system, gravity-controlled crystallization are made possible by a magnetic microgravity environment. In addition, in-situ and real-time observation and time-lapse imaging of crystal growth are feasible for over 200 solution samples independently. In this paper, we also report results of crystallization experiments for two protein samples. Crystals grown in the system exhibited magnetic orientation and showed higher and more homogeneous quality compared with the control crystals. The structural analysis reveals that making use of the magnetic microgravity during the crystallization process helps us to build a well-refined protein structure model, which has no significant structural differences with a control structure. Therefore, the system contributes to improvement in efficiency of structural analysis for "difficult" proteins, such as membrane proteins and supermolecular complexes.

Synthesis, structural, electronic and linear electro-optical features of new quaternary Ag{sub 2}Ga{sub 2}SiS{sub 6} compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Piasecki, M., E-mail: m.piasecki@ajd.czest.pl; Myronchuk, G.L.; Parasyuk, O.V.

For the first time phase equilibria and phase diagram of the AgGaS{sub 2}–SiS{sub 2} system were successfully explored by differential thermal and X-ray phase analysis methods. Crystal structure of low-temperature (LT) modification of Ag{sub 2}Ga{sub 2}SiS{sub 6} (LРў- Ag{sub 2}Ga{sub 2}SiS{sub 6}) was studied by X-ray powder method and it belongs to tetragonal space group I-42d, with unit cell parameters a=5.7164(4) Å, c=9.8023(7) Å, V=320.32(7) Å{sup 3}. Additional details regarding the crystal structure exploration are available at the web page Fachinformationszentrum Karlsruhe. X-ray photoelectron core-level and valence-band spectra were measured for pristine LРў- Ag{sub 2}Ga{sub 2}SiS{sub 6} crystal surface. Inmore » addition, the X-ray photoelectron valence-band spectrum of LРў-Ag{sub 2}Ga{sub 2}SiS{sub 6} was matched on a common energy scale with the X-ray emission S Kβ{sub 1,3} and Ga Kβ{sub 2} bands, which give information on the energy distribution of the S 3p and Ga 4p states, respectively. The presented X-ray spectroscopy results indicate that the valence S p and Ga p atomic states contribute mainly to the upper and central parts of the valence band of LРў-Ag{sub 2}Ga{sub 2}SiS{sub 6}, respectively, with a less significant contribution also to other valence-band regions. Band gap energy was estimated by measuring the quantum energy in the spectral range of the fundamental absorption. We have found that energy gap Eg is equal to 2.35 eV at 300 K. LT-Ag{sub 2}Ga{sub 2}SiS{sub 6} is a photosensitive material and reveals two spectral maxima on the curve of spectral photoconductivity spectra at λ{sub max1} =590 nm and λ{sub max2} =860 nm. Additionally, linear electro-optical effect of LT-Ag{sub 2}Ga{sub 2}SiS{sub 6} for the wavelengths of a cw He-Ne laser at 1150 nm was explored. - Graphical abstract: Manuscript present the technology of growth and investigation of properties a new quaternary compound Ag{sub 2}Ga{sub 2}SiS{sub 6} including the detailed study of the phase equilibria in the AgGaS{sub 2}–SiS{sub 2} system to determine the physico-chemical conditions of its formation. We examined crystal structure of the compound by X-ray powder method, its electronic structure by XPS method. Finally we have found these crystals like promising material for nonlinear optical, electrooptical and piezoelectric applications. - Highlights: • Phase diagram of the AgGaS{sub 2}–SiS{sub 2} system was successfully described at first time. • Crystal Ag{sub 2}Ga{sub 2}SiS{sub 6} was grown and its structure was determined. • Electronic structure and chemical bonding of the Ag{sub 2}Ga{sub 2}SiS{sub 6} crystal were examined by. • X-ray photoelectron spectroscopy (XPS) and X-ray emission spectroscopy (XES) methods. • Optical and photoelectrical properties were investigated.« less

High-speed prediction of crystal structures for organic molecules

NASA Astrophysics Data System (ADS)

Obata, Shigeaki; Goto, Hitoshi

2015-02-01

We developed a master-worker type parallel algorithm for allocating tasks of crystal structure optimizations to distributed compute nodes, in order to improve a performance of simulations for crystal structure predictions. The performance experiments were demonstrated on TUT-ADSIM supercomputer system (HITACHI HA8000-tc/HT210). The experimental results show that our parallel algorithm could achieve speed-ups of 214 and 179 times using 256 processor cores on crystal structure optimizations in predictions of crystal structures for 3-aza-bicyclo(3.3.1)nonane-2,4-dione and 2-diazo-3,5-cyclohexadiene-1-one, respectively. We expect that this parallel algorithm is always possible to reduce computational costs of any crystal structure predictions.

Ultrasensitive Silicon Photonic-Crystal Nanobeam Electro-Optical Modulator (Preprint)

DTIC Science & Technology

2013-10-01

and simulation results are presented for an ultralow switching energy, resonator based silicon-on-insulator (SOI) electro-optical modulator. The...joshua.hendrickson@wpafb.af.mil Abstract: Design and simulation results are presented for an ultralow switching energy, resonator based silicon-on...S. Fegadolli, J. E. B. Oliveira, V. R. Almeida, and A. Scherer, “Compact and low power consumption tunable photonic crystal nanobeam cavity,” 21

Vortex assisted solid-phase extraction of lead(II) using orthorhombic nanosized Bi2WO6 as a sorbent.

PubMed

Baghban, Neda; Yilmaz, Erkan; Soylak, Mustafa

2017-12-07

Nanosized single crystal orthorhombic Bi 2 WO 6 was synthesized by a hydrothermal method and used as a sorbent for vortex assisted solid phase extraction of lead(II). The crystal and molecular structure of the sorbent was examined using XRD, Raman, SEM and SEM-EDX analysis. Various parameters affecting extraction efficiency were optimized by using multivariate design. The effect of diverse ions on the extraction also was studied. Lead was quantified by flame atomic absorption spectrometry (FAAS). The recoveries of lead(II) from spiked samples (at a typical spiking level of 200-400 ng·mL -1 ) are >95%. Other figures of merit includes (a) a detection limit of 6 ng·mL -1 , (b) a preconcentration factor of 50, (c) a relative standard deviation of 1.6%, and (d) and adsorption capacity of 6.6 mg·g -1 . The procedure was successfully applied to accurate determination of lead in (spiked) pomegranate and water samples. Graphical abstract Nanosized single crystal orthorhombic Bi 2 WO 6 was synthesized and characterized by a hydrothermal method and used as a sorbent for vortex assisted solid phase extraction of lead(II). The procedure was successfully applied to accurate determination of lead in (spiked) pomegranate and water samples.

Two Keggin-type heteropolytungstates with transition metal as a central atom: Crystal structure and magnetic study with 2D-IR correlation spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chai, Feng; Chen, YiPing, E-mail: ypchen007@sina.com; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

2013-06-01

Two Keggin-type heteropolytungstates, [Co(phen)₃]₃[CoW₁₂O₄₀]·9H₂O 1 (phen=1,10-phenanthroline) and [Fe(phen)₃]₂[FeW₁₂O₄₀]·H₃O·H₂O 2, have been synthesized via the hydrothermal technique and characterized by single crystal X-ray diffraction analyses, IR, XPS, TG analysis, UV–DRS, XRD, thermal-dependent and magnetic-dependent 2D-COS IR (two-dimensional infrared correlation spectroscopy). Crystal structure analysis reveals that the polyanions in compound 1 are linked into 3D supramolecule through hydrogen bonding interactions between lattice water molecules and terminal oxygen atoms of polyanion units, and [Co(phen)₃]²⁺ cations distributed in the polyanion framework with many hydrogen bonding interactions. The XPS spectra indicate that all the Co atoms in 1 are +2 oxidation state, the Fe atomsmore » in 2 existing with +2 and +3 mixed oxidation states. - Graphical abstract: The magnetic-dependent synchronous 2D correlation IR spectra of 1 (a), 2 (b) over 0–50 mT in the range of 600–1000 cm⁻¹, the obvious response indicate two Keggin polyanions skeleton susceptible to applied magnetic field. Highlights: • Two Keggin-type heteropolytungstates with transition metal as a central atom has been obtained. • Compound 1 forms into 3D supramolecular architecture through hydrogen bonding between water molecules and polyanions. • Magnetic-dependent 2D-IR correlation spectroscopy was introduced to discuss the magnetism of polyoxometalate.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amdursky, Nadav; Gazit, Ehud; Rosenman, Gil, E-mail: gilr@eng.tau.ac.il

Highlights: Black-Right-Pointing-Pointer We observe lag-phase crystallization process in insulin. Black-Right-Pointing-Pointer The crystallization is a result of the formation of higher order oligomers. Black-Right-Pointing-Pointer The crystallization also changes the secondary structure of the protein. Black-Right-Pointing-Pointer The spectroscopic signature can be used for amyloid inhibitors assay. -- Abstract: Insulin, as other amyloid proteins, can form amyloid fibrils at certain conditions. The self-assembled aggregation process of insulin can result in a variety of conformations, starting from small oligomers, going through various types of protofibrils, and finishing with bundles of fibrils. One of the most common consensuses among the various self-assembly processes that aremore » suggested in the literature is the formation of an early stage nucleus conformation. Here we present an additional insight for the self-assembly process of insulin. We show that at the early lag phase of the process (prior to fibril formation) the insulin monomers self-assemble into ordered nanostructures. The most notable feature of this early self-assembly process is the formation of nanocrystalline nucleus regions with a strongly bound electron-hole confinement, which also change the secondary structure of the protein. Each step in the self-assembly process is characterized by an optical spectroscopic signature, and possesses a narrow size distribution. By following the spectroscopic signature we can measure the potency of amyloid fibrils inhibitors already at the lag phase. We further demonstrate it by the use of epigallocatechin gallate, a known inhibitor for insulin fibrils. The findings can result in a spectroscopic-based application for the analysis of amyloid fibrils inhibitors.« less

The General Base in the Thymidylate Synthase Catalyzed Proton Abstraction

PubMed Central

Ghosh, Ananda K.; Islam, Zahidul; Krueger, Jonathan; Abeysinghe, Don Thelma; Kohen, Amnon

2015-01-01

The enzyme thymidylate synthase (TSase), an important chemotherapeutic drug target, catalyzes the formation of 2′-deoxythymidine-5′-monophosphate (dTMP), a precursor of one of the DNA building blocks. TSase catalyzes a multi-step mechanism that includes the abstraction of a proton from the C5 of the substrate 2′-deoxyuridine-5′-monophosphate (dUMP). Previous studies on ecTSase proposed that an active-site residue, Y94 serves the role of the general base abstracting this proton. However, since Y94 is neither very basic, nor connected to basic residues, nor located close enough to the pyrimidine proton to be abstracted, the actual identity of this base remains enigmatic. Based on crystal structures, an alternative hypothesis is that the nearest potential proton-acceptor of C5 of dUMP is a water molecule that is part of a hydrogen bond (H-bond) network comprised of several water molecules and several protein residues including H147, E58, N177, and Y94. Here, we examine the role of the residue Y94 in the proton abstraction step by removing its hydroxyl group (Y94F mutant). We investigated the effect of the mutation on the temperature dependence of intrinsic kinetic isotope effects (KIEs) and found that these KIEs are more temperature dependent than those of the wild-type enzyme (WT). These results suggest that the phenolic –OH of Y94 is a component of the transition state for the proton abstraction step. The findings further support the hypothesis that no single functional group is the general base, but a network of bases and hydroxyls (from water molecules and tyrosine) sharing H-bonds across the active site can serve the role of the general base to remove the pyrimidine proton. PMID:25912171

Fabrication and characterization of cerium-doped barium titanate inverse opal by sol-gel method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin Yi; Zhu Yihua; Yang Xiaoling

Cerium-doped barium titanate inverted opal was synthesized from barium acetate contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a polystyrene (PS) opal. This procedure involves infiltration of precursors into the interstices of the PS opal template followed by hydrolytic polycondensation of the precursors to amorphous barium titanate and removal of the PS opal by calcination. The morphologies of opal and inverse opal were characterized by scanning electron microscope (SEM). The pores were characterized by mercury intrusion porosimetry (MIP). X-ray photoelectron spectroscopy (XPS) investigation showed the doping structure of cerium, barium and titanium. And powder X-ray diffraction allowsmore » one to observe the influence of doping degree on the grain size. The lattice parameters, crystal size and lattice strain were calculated by the Rietveld refinement method. The synthesis of cerium-doped barium titanate inverted opals provides an opportunity to electrically and optically engineer the photonic band structure and the possibility of developing tunable three-dimensional photonic crystal devices. - Graphical abstract: Cerium-doped barium titanate inverted opal was synthesized from barium acetate acid contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a PS opal, which involves infiltration of precursors into the interstices of the PS opal template and removal of the PS opal by calcination.« less

Lithium conductivity in an Li-bearing double-ring silicate mineral, sogdianite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, S.-H.; Hoelzel, M.; Forschungsneutronenquelle Heinz Maier-Leibnitz

The crystal structure of an Li-bearing double-ring silicate mineral, sogdianite ((Zr{sub 1.18}Fe{sup 3+} {sub 0.55}Ti{sub 0.24}Al{sub 0.03})(Y {sub 1.64},Na{sub 0.36})K{sub 0.85}[Li{sub 3}Si{sub 12}O{sub 30}], P6/mcc, a{approx}10.06 A, c{approx}14.30 A, Z=2), was investigated by neutron powder diffraction from 300 up to 1273 K. Rietveld refinements of displacement parameters revealed high anisotropic Li motions perpendicular to the crystallographic c-axis, indicating an exchange process between tetrahedral T2 and octahedral A sites. AC impedance spectra of a sogdianite single crystal (0.04x0.09x0.25 cm{sup 3}) show that the material is an ionic conductor with conductivity values of {sigma}=4.1x10{sup -5} S cm{sup -1} at 923 K andmore » 1.2x10{sup -3} S cm{sup -1} at 1219 K perpendicular to the c-axis, involving two relaxation processes with activation energies of 1.26(3) and 1.08(3) eV, respectively. - Graphical abstract: Structure of sogdianite with atomic displacement parameter (ADP) ellipsoids at 1273 K.« less

In search of the elusive IrB{sub 2}: Can mechanochemistry help?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Zhilin; Blair, Richard G.; Department of Physics, University of Central Florida, Orlando, FL 32816

The previously unknown hexagonal ReB{sub 2}-type IrB{sub 2} diboride and orthorhombic IrB monoboride phases were produced by mechanochemical syntheses. High energy ball milling of elemental Ir and B powder for 30 h, followed by annealing of the powder at 1050 °C for 48 h, resulted in the formation of the desired phases. Both traditional laboratory and high resolution synchrotron X-ray diffraction (XRD) analyses were used for phase identification of the synthesized powder. In addition to XRD, scanning electron microscopy and transmission electron microscopy were employed to further characterize the microstructure of the phases produced. - Graphical abstract: ReB{sub 2}-type IrB{submore » 2} and a new IrB have been successfully synthesized for the first time using mechanochemical method. Crystal structures of IrB{sub 2} and IrB were studied by synchrotron X-ray diffraction. Microstructures of the new phases were characterized by SEM and TEM. - Highlights: • ReB{sub 2}-type IrB{sub 2} and a new IrB have been synthesized by mechanochemical method. • Crystal structures of IrB{sub 2} and IrB were studied by synchrotron XRD. • Microstructures of the new phases were characterized by SEM and TEM.« less

Steam-assisted crystallization of TPA{sup +}-exchanged MCM-41 type mesoporous materials with thick pore walls

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hong Li; Zhang, Kun; Wang, Yi Meng, E-mail: ymwang@chem.ecnu.edu.cn

2012-07-15

Highlights: ► Mesoporous Ti-containing silica with thicker pore walls was synthesized. ► Ion-exchange and steam-assisted crystallization led to MCM-41/MFI composite. ► The introduction of Ti inhibited the formation of separated MFI particles. ► Lower temperature favored retaining mesoporous characteristics and morphology. -- Abstract: Hierarchical MCM-41/MFI composites were synthesized through ion-exchange of as-made MCM-41 type mesoporous materials with tetrapropylammonium bromide and subsequent steam-assisted recrystallization. The obtained samples were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis, FT-IR, {sup 1}H–{sup 13}C CP/MAS and nitrogen adsorption–desorption. The XRD patterns show thatmore » the MCM-41/MFI composite possesses both ordered MCM-41 phase and zeolite MFI phase. SEM and TEM images indicate that the recrystallized materials retained the mesoporous characteristics and the morphology of as-made mesoporous materials without the formation of bulky zeolite, quite different from the mechanical mixture of MCM-41 and MFI structured zeolite. Among others, lower recrystallization temperature and the introduction of the titanium to the parent materials are beneficial to preserve the mesoporous structure during the recrystallization process.« less

Likelihood-based modification of experimental crystal structure electron density maps

DOEpatents

Terwilliger, Thomas C [Sante Fe, NM

2005-04-16

A maximum-likelihood method for improves an electron density map of an experimental crystal structure. A likelihood of a set of structure factors {F.sub.h } is formed for the experimental crystal structure as (1) the likelihood of having obtained an observed set of structure factors {F.sub.h.sup.OBS } if structure factor set {F.sub.h } was correct, and (2) the likelihood that an electron density map resulting from {F.sub.h } is consistent with selected prior knowledge about the experimental crystal structure. The set of structure factors {F.sub.h } is then adjusted to maximize the likelihood of {F.sub.h } for the experimental crystal structure. An improved electron density map is constructed with the maximized structure factors.

Interplay between crystal and magnetic structures in YFe{sub 2}(H{sub α}D{sub 1−α}){sub 4.2} compounds studied by neutron diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paul-Boncour, V., E-mail: paulbon@icmpe.cnrs.fr; Guillot, M.; Isnard, O.

We report a detailed magnetic structure investigation of YFe{sub 2}(H{sub α}D{sub 1−α}){sub 4.2} (α=0, 0.64, 1) compounds presenting a strong (H,D) isotope effect by neutron diffraction and Mössbauer spectroscopy analysis. They crystallize in the same monoclinic structure (Pc space group) with 8 inequivalent Fe sites having different H(D) environment. At low temperature, the compounds are ferromagnetic (FM) and show an easy magnetization axis perpendicular to the b axis and only slightly tilted away from the c axis. Upon heating, they display a first order transition from a ferromagnetic towards an antiferromagnetic (AFM) structure at T{sub M0} which is sensitive tomore » the H/D isotope nature. The AFM cell is described by doubling the crystal cell along the monoclinic b axis. It presents an unusual coexistence of non magnetic Fe layer sandwiched by two thicker ferromagnetic Fe layers which are antiparallel to each other. This FM-AFM transition is driven by the loss of ordered moment on one Fe site (Fe7) through an itinerant electron metamagnetic (IEM) behaviour. The key role of the Fe7 position is assigned to both its hydrogen rich atomic environment and its geometric position. Above T{sub M0} a field induced metamagnetic transition is observed from the AFM towards the FM structure accompanied by a cell volume increase. Both thermal and magnetic field dependence of the magnetic structure are found strongly related to the anisotropic cell distortion induced by (H,D) order in interstitial sites. - Graphical abstract: Representation of the FM-AFM magnetic structures of YFe{sub 2}D{sub 4.2} deuteride. - Highlights: • YFe{sub 2}(H,D){sub 4.2} compounds undergoes a isotope sensitive FM-AFM transition at T{sub M0}. • The FM structure is formed of Fe moments perpendicular to the monoclinic b axis. • AFM structure is formed by antiparallel Fe layers separated by non-magnetic Fe layer. • One Fe site among eight loses its moment at T{sub M0} due to larger Fe–H bonding. • Magnetic properties are driven by the monoclinic distortion induced by D order.« less

Type A-B carbonate chlorapatite synthesized at high pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fleet, Michael E.; Liu, Xi

2008-09-15

Sodium-bearing type A-B carbonate chlorapatites {l_brace}CCLAP; Ca{sub 10-(y+z)}Na{sub y}{open_square}{sub z}[(PO{sub 4}){sub 6-(y+2z)}(CO{sub 3}){sub y+2z}][Cl{sub 2-=} 2{sub x}(CO{sub 3}){sub x}], with x{approx}y{approx}4z{approx}0.4{r_brace} have been synthesized from carbonate-rich melts at 1350-1000 deg. C and 1.0 GPa, and investigated by single-crystal X-ray structure and FTIR spectroscopy. Typical crystal and compositional data are: a=9.5321(4) A, c=6.8448(3) A, space group P6{sub 3}/m, R=0.027, R{sub w}=0.025, x=0.37(3), y=0.57(2). Crystal-chemical features and FTIR spectra are similar to Na-bearing type A-B carbonate hydroxyapatites (CHAP) and fluorapatites (CFAP) reported recently. The molar amounts of Na and channel (type A) carbonate maintain a near 1:1 ratio in all three compositionmore » series, confirming that the Na cation and A and B carbonate ion substituents exist as a defect cluster within the apatite matrix, to facilitate charge compensation and spatial accommodation. Uptake of carbonate is significantly lower in CCLAP than in CHAP for similar conditions of crystal synthesis. - Graphical abstract: Defect cluster (blue) of A carbonate ion in apatite channel, Na{sup +} cation, and B carbonate ion replacing phosphate group, in carbonate chlorapatite synthesized at high pressure.« less

The structural coloration of textile materials using self-assembled silica nanoparticles.

PubMed

Gao, Weihong; Rigout, Muriel; Owens, Huw

2017-01-01

The work presented investigates how to produce structural colours on textile materials by applying a surface coating of silica nanoparticles (SNPs). Uniform SNPs with particle diameters in a controlled micron size range (207-350 nm) were synthesized using a Stöber-based solvent varying (SV) method which has been reported previously. Photonic crystals (PCs) were formed on the surface of a piece of textile fabric through a process of natural sedimentation self-assembly of the colloidal suspension containing uniform SNPs. Due to the uniformity and a particular diameter range of the prepared SNPs, structural colours were observed from the fabric surface due to the Bragg diffraction of white light with the ordered structure of the silica PCs. By varying the mean particle diameter, a wide range of spectral colours from red to blue were obtained. The comparison of structural colours on fabrics and on glasses suggests that a smooth substrate is critical when producing materials with high colour intensity and spatial uniformity. This work suggested a promising approach to colour textile materials without the need for traditional dyes and/or pigments. Graphical abstract.

Color-tunable up-conversion emission in Y2O3:Yb3+, Er3+ nanoparticles prepared by polymer complex solution method

PubMed Central

2013-01-01

Abstract Powders of Y2O3 co-doped with Yb3+ and Er3+ composed of well-crystallized nanoparticles (30 to 50 nm in diameter) with no adsorbed ligand species on their surface are prepared by polymer complex solution method. These powders exhibit up-conversion emission upon 978-nm excitation with a color that can be tuned from green to red by changing the Yb3+/Er3+ concentration ratio. The mechanism underlying up-conversion color changes is presented along with material structural and optical properties. PACS 42.70.-a, 78.55.Hx, 78.60.-b PMID:23522083

Structural, electronic and magnetic properties of layered REB{sub 2}C compounds (RE=Dy, Tm, Lu)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babizhetskyy, Volodymyr, E-mail: v.babizhetskyy@googlemail.com; Department of Inorganic Chemistry, Ivan Franko National University of L'viv, Kyryla and Mefodiya Str. 6, UA-79005 Lviv; Simon, Arndt

2012-07-15

The crystal structure of LuB{sub 2}C has been determined from single crystal and powder X-ray diffraction data. It crystallizes in the orthorhombic space group Pbam (a=6.7429(1) A, b=6.7341(1) A, c=3.5890(1) A, Z=4, R1=0.024 (wR2=0.059) for 436 reflections with I{sub o}>2{sigma}(I{sub o})). The compounds REB{sub 2}C (RE=Y, Tb-Lu) are isotypic. The boron and carbon atoms form infinite, planar two-dimensional nets which alternate with sheets of rare-earth metal atoms. Inside the nonmetal atom nets, a coloring with fused B{sub 2}C{sub 2} rhombuses and B{sub 5}C{sub 2} heptagons is proposed, supported by NMR experiments and density functional theory calculations. The calculated density ofmore » states of LuB{sub 2}C indicates this compound to be metallic. The magnetic properties of the isotypic compound TmB{sub 2}C, has been measured in the temperature range 2 K3 T a metamagnetic transition is encountered. The temperature dependence of the electrical resistivity proves the metallic character of the TmB{sub 2}C compound as well as the AFM ordering. - Graphical abstract: The crystal structure of LuB{sub 2}C has been determined from single crystal and powder X-ray diffraction data. It crystallizes in the orthorhombic space group Pbam. The compounds REB{sub 2}C (RE=Y, Tb-Lu) are isotypic. The boron and carbon atoms form infinite, planar two-dimensional nets which alternate with sheets of rare-earth metal atoms. Inside the nonmetal atom nets, a coloring with fused B{sub 2}C{sub 2} rhombuses and B{sub 5}C{sub 2} heptagons is proposed, supported by NMR experiments and density functional theory calculations. The magnetic properties of the isotypic compound TmB{sub 2}C, has been measured in the temperature range 2 K3 T a metamagnetic transition is encountered. The temperature dependence of the electrical resistivity proves the metallic character of the TmB{sub 2}C compound as well as the AFM ordering. Highlights: Black-Right-Pointing-Pointer LuB{sub 2}C compound crystallizes in orthorhombic symmetry. Black-Right-Pointing-Pointer In the structure the B{sub 2}C layers are stacked directly on top of each other. Black-Right-Pointing-Pointer A coloring with fused B{sub 2}C{sub 2} rhombuses and B{sub 5}C{sub 2} heptagons is proposed. Black-Right-Pointing-Pointer The coloring is supported by NMR experiments and theoretical calculations. Black-Right-Pointing-Pointer TmB{sub 2}C undergoes an antiferromagnetic transition at T{sub N}=12 K at elevated fields.« less

Polymer-Induced Heteronucleation for Protein Single Crystal Growth: Structural Elucidation of Bovine Liver Catalase and Concanavalin A Forms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foroughi, Leila M.; Kang, You-Na; Matzger, Adam J.

Obtaining single crystals for X-ray diffraction remains a major bottleneck in structural biology; when existing crystal growth methods fail to yield suitable crystals, often the target rather than the crystallization approach is reconsidered. Here we demonstrate that polymer-induced heteronucleation, a powerful technique that has been used for small molecule crystallization form discovery, can be applied to protein crystallization by optimizing the heteronucleant composition and crystallization formats for crystallizing a wide range of protein targets. Applying these advances to two benchmark proteins resulted in dramatically increased crystal size, enabling structure determination, for a half century old form of bovine liver catalasemore » (BLC) that had previously only been characterized by electron microscopy, and the discovery of two new forms of concanavalin A (conA) from the Jack bean and accompanying structural elucidation of one of these forms.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, H.K.; Science Center for Phase Diagram and Materials Design and Manufacture, Central South University, Changsha, Hunan 410083; Cai, G.M., E-mail: caigemei@csu.edu.cn

Two novel borate compounds MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8}, have been synthesized via solid-state reactions, and their crystal structures have been solved and refined from powder X-ray diffraction data. The compound MgInBO{sub 4}, which was obtained at 1190 °C, belongs to the warwickite family. It crystallizes in the Pnma space group (no. 62) with a=9.5443(1) Å, b=3.2771(1) Å, c=9.5228(1) Å, and Z=4. The fundamental building units are liner –Mg(In)O{sub 6}–[In(Mg)]{sub 2}O{sub 10}–Mg(In)O{sub 6}– chains and isolated BO{sub 3} triangles. The low-temperature phase, MgIn{sub 7/8}B{sub 7/8}O{sub 29/8}, whose crystal structure is solved ab initio by the charge-flipping method withmore » standard chemical formula MgInBO{sub 4}, was prepared at 1080 °C. It crystallizes in the P12{sub 1}/n1 space group (no. 14) with a=17.0976(1) Å, b=3.2504(1) Å, c=5.3387(1) Å, β=96.0829(3)°, and Z=4. The structure of MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} contains [In(2)/Mg(2)]{sub 2}O{sub 10} groups, –MgO{sub 6}–InO{sub 6}– infinite ribbons and isolated BO{sub 3} triangles. The experiments and the differential thermal analysis (DTA) show the decompositions of MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} happen at about 1220 °C and 1180 °C, respectively. The comparative crystal chemistry from MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} to MgInBO{sub 4} has been discussed. Infrared spectra and UV–vis diffuse reflectance spectra of MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} were measured. - Graphical abstract: The structural transformation from the monoclinic MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} (P12{sub 1}/n1) to the orthorhombic MgInBO{sub 4} (Pnma). - Highlights: • Two novel borate compounds MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} have been synthesized via solid-state reactions for the first time. • The crystal structures of MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} have been solved and refined from powder X-ray diffraction data. • The possible crystal chemical analysis from MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} to MgInBO{sub 4} is discussed. • Infrared spectra and UV–vis diffuse reflectance spectra of MgInBO{sub 4} and MgIn{sub 7/8}B{sub 7/8}O{sub 29/8} have been measured.« less

Physical and Structural Studies on the Cryo-cooling of Insulin Crystals

NASA Technical Reports Server (NTRS)

Lovelace, J.; Bellamy, H.; Snell, E. H.; Borgstahl, G.

2003-01-01

Reflection profiles were analyzed from microgravity-(mg) and earth-grown insulin crystals to measure mosaicity (h) and to reveal mosaic domain structure and composition. The effects of cryocooling on single and multi-domain crystals were compared. The effects of cryocooling on insulin structure were also re-examined. Microgravity crystals were larger, more homogeneous, and more perfect than earth crystals. Several mg crystals contained primarily a single mosaic domain with havg of 0.005deg. The earth crystals varied in quality and all contained multiple domains with havg of 0.031deg. Cryocooling caused a 43-fold increase in h for mg crystals (havg=0.217deg) and an %fold increase for earth crystals (havg=0.246deg). These results indicate that very well-ordered crystals are not completely protected from the stresses associated with cryocooling, especially when structural perturbations occur. However, there were differences in the reflection profiles. For multi-mosaic domain crystals, each domain individually broadened and separated from the other domains upon cryo-cooling. Cryo-cooling did not cause an increase in the number of domains. A crystal composed of a single domain retained this domain structure and the reflection profiles simply broadened. Therefore, an improved signal-to-noise ratio for each reflection was measured from cryo-cooled single domain crystals relative to cryo-cooled multi-domain crystals. This improved signal, along with the increase in crystal size, facilitated the measurement of the weaker high- resolution reflections. The observed broadening of reflection profiles indicates increased variation in unit cell dimensions which may be linked to cryo-cooling-associated structural changes and disorder.

Crystal structure of minoxidil at low temperature and polymorph prediction.

PubMed

Martín-Islán, Africa P; Martín-Ramos, Daniel; Sainz-Díaz, C Ignacio

2008-02-01

An experimental and theoretical investigation on crystal forms of the popular and ubiquitous pharmaceutical Minoxidil is presented here. A new crystallization method is presented for Minoxidil (6-(1-piperidinyl)-2,4-pyrimidinediamide 3-oxide) in ethanol-poly(ethylene glycol), yielding crystals with good quality. The crystal structure is determined at low temperature, with a final R value of 0.035, corresponding to space group P2(1) (monoclinic) with cell dimensions a = 9.357(1) A, b = 8.231(1) A, c = 12.931(2) A, and beta = 90.353(4) degrees . Theoretical calculations of the molecular structure of Minoxidil are set forward using empirical force fields and quantum-mechanical methods. A theoretical prediction for Minoxidil crystal structure shows many possible polymorphs. The predicted crystal structures are compared with X-ray experimental data obtained in our laboratory, and the experimental crystal form is found to be one of the lowest energy polymorphs.

Selective Se-for-S substitution in Cs-bearing uranyl compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru; Tyumentseva, Olga S.; Krivovichev, Sergey V.

Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se), which crystallizes in tetragonal system, P-42{sub 1}m, a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å{sup 3}. Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]more » (T= S, Se) compounds are based upon the [(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]{sup 2-} layers of corner-sharing uranyl pentagonal bipyramids and TO{sub 4} tetrahedra. The layers contain two types of tetrahedral sites: T1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded T2 site. Crystallization in the pure Se system starts with the formation of Cs{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) crystals, its subsequent dissolution and formation of Cs{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. - Graphical abstract: Nine phases representing the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) solid solution series with variable amount of S and Se have been prepared by isothermal evaporation from aqueous solutions and characterized using a number of experimental and theoretical techniques. No immiscibility is observed between the pure sulfate and selenate compounds. The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded 4-connected site. - Highlights: • Single crystals of novel mixed sulfate-selenate uranyl oxysalts were prepared by evaporation method. • Topological analysis and information-based complexity calculations were used for structure description. • The selective Se-for-S substitution was observed. • Evolution of phase formation in the aqueous Cs{sup +}–UO{sub 2}{sup 2+}–SO{sub 4}{sup 2–}–SeO{sub 4}{sup 2–} system was analyzed.« less

High-throughput crystallization screening.

PubMed

Skarina, Tatiana; Xu, Xiaohui; Evdokimova, Elena; Savchenko, Alexei

2014-01-01

Protein structure determination by X-ray crystallography is dependent on obtaining a single protein crystal suitable for diffraction data collection. Due to this requirement, protein crystallization represents a key step in protein structure determination. The conditions for protein crystallization have to be determined empirically for each protein, making this step also a bottleneck in the structure determination process. Typical protein crystallization practice involves parallel setup and monitoring of a considerable number of individual protein crystallization experiments (also called crystallization trials). In these trials the aliquots of purified protein are mixed with a range of solutions composed of a precipitating agent, buffer, and sometimes an additive that have been previously successful in prompting protein crystallization. The individual chemical conditions in which a particular protein shows signs of crystallization are used as a starting point for further crystallization experiments. The goal is optimizing the formation of individual protein crystals of sufficient size and quality to make them suitable for diffraction data collection. Thus the composition of the primary crystallization screen is critical for successful crystallization.Systematic analysis of crystallization experiments carried out on several hundred proteins as part of large-scale structural genomics efforts allowed the optimization of the protein crystallization protocol and identification of a minimal set of 96 crystallization solutions (the "TRAP" screen) that, in our experience, led to crystallization of the maximum number of proteins.

High-throughput crystal-optimization strategies in the South Paris Yeast Structural Genomics Project: one size fits all?

PubMed

Leulliot, Nicolas; Trésaugues, Lionel; Bremang, Michael; Sorel, Isabelle; Ulryck, Nathalie; Graille, Marc; Aboulfath, Ilham; Poupon, Anne; Liger, Dominique; Quevillon-Cheruel, Sophie; Janin, Joël; van Tilbeurgh, Herman

2005-06-01

Crystallization has long been regarded as one of the major bottlenecks in high-throughput structural determination by X-ray crystallography. Structural genomics projects have addressed this issue by using robots to set up automated crystal screens using nanodrop technology. This has moved the bottleneck from obtaining the first crystal hit to obtaining diffraction-quality crystals, as crystal optimization is a notoriously slow process that is difficult to automatize. This article describes the high-throughput optimization strategies used in the Yeast Structural Genomics project, with selected successful examples.

Diagnosing the Internal Architecture of Zeolite Ferrierite

PubMed Central

Schmidt, Joel E.; Hendriks, Frank C.; Lutz, Martin; Post, L. Christiaan; Fu, Donglong

2017-01-01

Abstract Large crystals of zeolite ferrierite (FER) are important model systems for spatially resolved catalysis and diffusion studies, though there is considerable variation in crystal habit depending on the chemical composition and employed synthesis conditions. A synergistic combination of techniques has been applied, including single crystal X‐ray diffraction, high‐temperature in situ confocal fluorescence microscopy, fluorescent probe molecules, wide‐field microscopy and atomic force microscopy to unravel the internal architecture of three distinct FER zeolites. Pyrolyzed template species can be used as markers for the 8‐membered ring direction as they are trapped in the terraced roof of the FER crystals. This happens as the materials grow in a layer‐by‐layer, defect‐free manner normal to the large crystal surface, and leads to a facile method to diagnose the pore system orientation, which avoids tedious single crystal X‐ray diffraction experiments. PMID:28809081

Structural, optical and magnetic properties of gadolinium sesquioxide nanobars synthesized via thermal decomposition of gadolinium oxalate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manigandan, R.; Giribabu, K.; Suresh, R.

2013-10-15

Graphical abstract: - Highlights: • The cubic Gd{sub 2}O{sub 3} nanobars are synthesized by decomposition of C{sub 6}H{sub 20}Gd{sub 2}O{sub 22}. • The nanoparticles are rectangular bar shape with high porous surface. • The combination of magnetic and optical properties within a single particle. • The Gd{sub 2}O{sub 3} nanobars have tailorable nanostructure, wide bandgap and are paramagnetic. - Abstract: Gadolinium oxide nanobars were obtained by thermal decomposition of gadolinium oxalate, which was synthesized by the chemical precipitation method along with glycerol. The functional group analysis and formation of gadolinium oxide from gadolinium oxalate were characterized by the Fourier transformmore » infrared spectroscopy and thermo gravimetric analyzer. The crystal structure, average crystallite size, and lattice parameter were analyzed by X-ray diffraction technique. Moreover, Raman shifts, elemental composition and morphology of the gadolinium oxide was widely investigated by the laser Raman microscope, X-ray photoelectron spectroscopy, FE-SEM-EDAX and HR-TEM, respectively. Furthermore, the optical properties like band gap, absorbance measurement of the gadolinium oxide were extensively examined. In addition, the paramagnetic property of gadolinium oxide nanobars was explored by the vibrating sample magnetometer.« less

A novel structure of gel grown strontium cyanurate crystal and its structural, optical, electrical characterization

NASA Astrophysics Data System (ADS)

Divya, R.; Nair, Lekshmi P.; Bijini, B. R.; Nair, C. M. K.; Gopakumar, N.; Babu, K. Rajendra

2017-12-01

Strontium cyanurate crystals with novel structure and unique optical property like mechanoluminescence have been grown by conventional gel method. Transparent crystals were obtained. The single crystal X-ray diffraction analysis reveals the exquisite structure of the grown crystal. The crystal is centrosymmetric and has a three dimensional polymeric structure. The powder X ray diffraction analysis confirms its crystalline nature. The functional groups present in the crystal were identified by Fourier transform infrared spectroscopy. Elemental analysis confirmed the composition of the complex. A study of thermal properties was done by thermo gravimetric analysis and differential thermal analysis. The optical properties like band gap, refractive index and extinction coefficient were evaluated from the UV visible spectral analysis. The etching study was done to reveal the dislocations in the crystal which in turn explains mechanoluminescence emission. The mechanoluminescence property exhibited by the crystal makes it suitable for stress sensing applications. Besides being a centrosymmetric crystal, it also exhibits NLO behavior. Dielectric properties were studied and theoretical calculations of Fermi energy, valence electron plasma energy, penn gap and polarisability have been done.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Sixuan; Latturner, Susan E., E-mail: latturner@chem.fsu.edu

The intermetallic compounds RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} (RE=Pr{sub ,} Nd) were synthesized from the reaction of germanium and aluminum in RE/Co eutectic flux. These phases crystallize with the Nd{sub 6}Co{sub 5}Ge{sub 2.2} structure type in hexagonal space group P-6m2 (a=9.203(2)Å, c=4.202(1) Å, R{sub 1}=0.0109 for Pr{sub 6}Co{sub 5}Ge{sub 1.80}Al{sub 2.20}; and a=9.170(3) Å, c=4.195(1) Å, R{sub 1}=0.0129 for Nd{sub 6}Co{sub 5}Ge{sub 1.74}Al{sub 2.26}). The structure features chains of face-sharing Ge@RE{sub 9} clusters intersecting hexagonal cobalt nets linked by aluminum atoms. Magnetic susceptibility measurements indicate that both phases exhibit ferromagnetic ordering of the cobalt layers with T{sub C} in themore » range of 130–140 K. The magnetic moments of the rare earth ions order at lower temperature (30–40 K). Magnetic measurements on oriented crystals of Nd{sub 6}Co{sub 5}Ge{sub 1.74}Al{sub 2.26} show a strong preference of the moments to order along the c-axis. - Graphical abstract: RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} (RE=Pr{sub ,} Nd) were grown as large crystals from reactions of Ge and Al in RE/Co eutectic melts. Magnetic measurements indicate ordering of the 2-D cobalt nets at 130–140 K, and ordering of the rare earth moments at 30–40 K. Display Omitted - Highlights: • RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} (RE=Pr{sub ,} Nd) grown as large crystals from RE/Co eutectic flux. • RE{sub 6}Co{sub 5}Ge{sub 1+x}Al{sub 3−x} structure features hexagonal cobalt nets stacked along c-axis. • Cobalt layers order ferromagnetically with T{sub c}=130–140 K. • Rare earth magnetic moments order at low temperature (30–40 K).« less

Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4}: Novel keesterite type solid solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez-Vergara, F., E-mail: fer_martina@u.uchile.cl; Galdamez, A., E-mail: agaldamez@uchile.cl; Manriquez, V.

2013-02-15

A new family of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} chalcogenides has been synthesized by conventional solid-state reactions at 850 Degree-Sign C. The reactions products were characterized by powder X-ray diffraction (XRD), energy-dispersive X-ray analysis (SEM-EDS), Raman spectroscopy and magnetic susceptibility. The crystal structures of two members of the solid solution series Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4} have been determined by single-crystal X-ray diffraction. Both phases crystallize in the tetragonal keesterite-type structure (space group I4{sup Macron }). The distortions of the tetrahedral volume of Cu{sub 2}Mn{sub 0.4}Co{sub 0.6}SnS{sub 4} and Cu{sub 2}Mn{sub 0.2}Co{sub 0.8}SnS{sub 4}more » were calculated and compared with the corresponding differences in the Cu{sub 2}MnSnS{sub 4} (stannite-type) end-member. The compounds show nearly the same Raman spectral features. Temperature-dependent magnetization measurements (ZFC/FC) and high-temperature susceptibility indicate that these solid solutions are antiferromagnetic. - Graphical abstract: View along [100] of the Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} structure showing tetrahedral units and magnetic measurement ZFC-FC at 500 Oe. The insert shows the 1/{chi}-versus-temperature plot fitted by a Curie-Weiss law. Highlights: Black-Right-Pointing-Pointer Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} solid solutions belong to the family of compounds adamantine. Black-Right-Pointing-Pointer Resolved single crystals of the solid solutions have space group I4{sup Macron }. Black-Right-Pointing-Pointer The distortion of the tetrahedral volume of Cu{sub 2}Mn{sub 1-x}Co{sub x}SnS{sub 4} were calculated. Black-Right-Pointing-Pointer These solid solutions are antiferromagnetic.« less

Well-aligned polycrystalline lanthanum silicate oxyapatite grown by reactive diffusion between solid La{sub 2}SiO{sub 5} and gases [SiO+1/2O{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.jp; Hasegawa, Ryo; Kitagawa, Takuya

2016-03-15

The c-axis-oriented polycrystalline lanthanum silicate oxyapatite, La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} (□ denotes a vacancy in the Si site), was successfully prepared by the reactive diffusion between randomly grain-oriented La{sub 2}SiO{sub 5} polycrystal and [SiO+1/2O{sub 2}] gases at 1873 K in Ar atmosphere. The polycrystal was characterized using optical microscopy, scanning electron microscopy equipped with energy dispersive X-ray spectroscopy, micro-Raman spectroscopy, X-ray diffractometry, and impedance spectroscopy. The crystal structure (space group P6{sub 3}/m) showed the deficiency of Si site at ca. 1.9%. The bulk oxide-ion conductivity along the grain-alignment direction steadily increased from 9.2 × 10{sup −3} to 1.17 ×more » 10{sup −2} S/cm with increasing temperature from 923 to 1073 K. The activation energy of conduction was 0.23(2) eV. - Graphical abstract: We have successfully prepared the highly c-axis-oriented polycrystalline La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} by the reactive diffusion between randomly grain-oriented La{sub 2}SiO{sub 5} polycrystal and [SiO + 1/2O{sub 2}] gases at 1873 K in Ar atmosphere. The crystal structure (space group P6{sub 3}/m) showed the deficiency of Si site of ca. 1.9%. - Highlights: • The c-axis-oriented polycrystalline La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} is successfully prepared. • Crystal structure of La{sub 9.48}(Si{sub 5.89}□{sub 0.11})O{sub 26} is determined by single-crystal XRD. • The polycrystal shows relatively high oxide ion conductivity along the common c-axis. • Reactive diffusion is successfully used for the preparation of grain-aligned ceramics.« less

Supplement request for Support of MRS Symposium (PECASE: Active Microstructured Polymer Systems)

DTIC Science & Technology

2015-07-06

materials (e.g., gels, polymers, liquids , liquid crystals and photosensitive materials) that can change shape in a controlled response to stimuli. These...Rogers1. 1, , University of Illinois, Urbana, Illinois, USA. Show Abstract 8:45 AM - *XX1.02 New Wonders of Nafion : Shape Memory, Temperature Memory... Liquid Crystal Institute, Kent State University, Kent, Ohio, USA; 5, Department of Electrical and Computer Engineering, University of Idaho, Moscow

Inorganic Crystal Structure Database (ICSD)

National Institute of Standards and Technology Data Gateway

SRD 84 FIZ/NIST Inorganic Crystal Structure Database (ICSD) (PC database for purchase)   The Inorganic Crystal Structure Database (ICSD) is produced cooperatively by the Fachinformationszentrum Karlsruhe(FIZ) and the National Institute of Standards and Technology (NIST). The ICSD is a comprehensive collection of crystal structure data of inorganic compounds containing more than 140,000 entries and covering the literature from 1915 to the present.

Microgravity

NASA Image and Video Library

1992-06-25

Zeolites are crystalline aluminosilicates that have complex framework structures. However, there are several features of zeolite crystals that make unequivocal structure determinations difficult. The acquisition of reliable structural information on zeolites is greatly facilitated by the availability of high-quality specimens. For structure determinations by conventional diffraction techniques, large single-crystal specimens are essential. Alternatively, structural determinations by powder profile refinement methods relax the constraints on crystal size, but still require materials with a high degree of crystalline perfection. Studies conducted at CAMMP (Center for Advanced Microgravity Materials Processing) have demonstrated that microgravity processing can produce larger crystal sizes and fewer structural defects relative to terrestrial crystal growth. Principal Investigator: Dr. Albert Sacco

Zeolites

NASA Technical Reports Server (NTRS)

1992-01-01

Zeolites are crystalline aluminosilicates that have complex framework structures. However, there are several features of zeolite crystals that make unequivocal structure determinations difficult. The acquisition of reliable structural information on zeolites is greatly facilitated by the availability of high-quality specimens. For structure determinations by conventional diffraction techniques, large single-crystal specimens are essential. Alternatively, structural determinations by powder profile refinement methods relax the constraints on crystal size, but still require materials with a high degree of crystalline perfection. Studies conducted at CAMMP (Center for Advanced Microgravity Materials Processing) have demonstrated that microgravity processing can produce larger crystal sizes and fewer structural defects relative to terrestrial crystal growth. Principal Investigator: Dr. Albert Sacco

From molecule to solid: The prediction of organic crystal structures

NASA Astrophysics Data System (ADS)

Dzyabchenko, A. V.

2008-10-01

A method for predicting the structure of a molecular crystal based on the systematic search for a global potential energy minimum is considered. The method takes into account unequal occurrences of the structural classes of organic crystals and symmetry of the multidimensional configuration space. The programs of global minimization PMC, comparison of crystal structures CRYCOM, and approximation to the distributions of the electrostatic potentials of molecules FitMEP are presented as tools for numerically solving the problem. Examples of predicted structures substantiated experimentally and the experience of author’s participation in international tests of crystal structure prediction organized by the Cambridge Crystallographic Data Center (Cambridge, UK) are considered.

Crystals of Janus colloids at various interaction ranges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Preisler, Z.; Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht; Vissers, T.

We investigate the effect of interaction range on the phase behaviour of Janus particles with a Kern-Frenkel potential. Specifically, we study interaction ranges Δ = 0.1σ, 0.3σ, 0.4σ, 0.5σ with σ the particle diameter, and use variable box shape simulations to predict crystal structures. We found that changing the interaction range beyond 0.2σ drastically increases the variety of possible crystal structures. In addition to close-packed structures, we find body-centered tetragonal and AA-stacked hexagonal crystals, as well as several lamellar crystals. For long interaction ranges and low temperatures, we also observe an extremely large number of metastable structures which compete withmore » the thermodynamically stable ones. These competing structures hinder the detection of the lowest-energy crystal structures, and are also likely to interfere with the spontaneous formation of the ground-state structure. Finally, we determine the gas-liquid coexistence curves for several interaction ranges, and observe that these are metastable with respect to crystallization.« less

The nature of the mineral component of bone and the mechanism of calcification.

PubMed

Glimcher, M J

1987-01-01

From the physical chemical standpoint, the formation of a solid phase of Ca-P in bone represents a phase transformation, a process exemplified by the formation of ice from water. Considering the structural complexity and abundance of highly organized macromolecules in the cells and extracellular tissue spaces of mineralized tissues generally and in bone particularly, it is inconceivable that this phase transformation occurs by homogeneous nucleation, i.e., without the active participation of an organic component acting as a nucleator. This is almost surely true in biologic mineralization in general. Electron micrographs and low-angle neutron and X-ray diffraction studies clearly show that calcification of collagen fibrils occurs in an extremely intimate and highly organized fashion: initiation of crystal formation within the collagen fibrils in the hole zone region, with the long axes (c-axis) of the crystals aligned roughly parallel to the long axis of the fibril within which they are located. Crystals are initially formed in hole zone regions within individual fibrils separated by unmineralized regions. Calcification is initiated in spatially distinct nucleation sites. This indicates that such regions within a single, undirectional fibril represents independent sites for heterogeneous nucleation. Clearly, sites where mineralization is initiated in adjacent collagen fibrils are even further separated, emphasizing even more clearly that the process of progressive calcification of the collagen fibrils and therefore of the tissue is characterized principally by the presence of increasing numbers of independent nucleation sites within additional hole zone regions of the collagen fibrils. The increase in the mass of Ca-P apatite accrues principally by multiplication of more crystals, mostly by secondary nucleation from the crystals initially deposited in the hole zone region. Very little additional growth of the crystals occurs with time, the additional increase in mineral mass being principally the result of increase in the number of crystals (multiplication), not size of the crystals (crystal growth). The crystals within the collagen fibers grow in number and possibly in size to extend into the overlap zone of the collagen fibrils ("pores") so that all of the available space within the fibrils, which has possibly expanded in volume from its uncalcified level, is eventually occupied by the mineral crystals. It must be recognized that the calcification of separate tissue components and compartments (collagen, mitochondria, matrix vesicles) must be an independent physical chemical event.(ABSTRACT TRUNCATED AT 400 WORDS)

Exploring Solid-State Structure and Physical Properties: A Molecular and Crystal Model Exercise

ERIC Educational Resources Information Center

Bindel, Thomas H.

2008-01-01

A crystal model laboratory exercise is presented that allows students to examine relations among the microscopic-macroscopic-symbolic levels, using crystalline mineral samples and corresponding crystal models. Students explore the relationship between solid-state structure and crystal form. Other structure-property relationships are explored. The…

DOE Office of Scientific and Technical Information (OSTI.GOV)

Che, Guang-Bo, E-mail: guangboche@jlnu.edu.cn; Liu, Shu-Yu; Zhang, Qing

Four new lanthanide complexes [Ln(O–NCP){sub 2}(NO{sub 3})]{sub n} based on multifunctional N,O-donor ligand 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (O–HNCP) and Ln(NO{sub 3}){sub 3}·6H{sub 2}O (Ln=Nd(1), La(2), Sm(3), Eu(4)) have been achieved under hydrothermal conditions and characterized by elemental analyses, infrared spectra and single crystal X-ray diffraction. Structural analyses revealed that all of these four complexes possess similar two-dimensional layer structures. In addition, thermal stability and luminescent properties of these complexes were also investigated. - Graphical abstract: A series of lanthanide(III) coordination polymers with intriguing structures based on 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline ligand have been hydrothermally synthesized. The thermal stabilities and photoluminescence properties of these complexes have beenmore » investigated. - Highlights: • Four lanthanide(III) complexes have been hydrothermally synthesized. • The N,O-donor O–HNCP was used as the ligand. • TGA and PL properties of complexes 1–4 have been investigated.« less

Direct solar pumping of semiconductor lasers: A feasibility study

NASA Technical Reports Server (NTRS)

Anderson, Neal G.

1991-01-01

The primary goals of the feasibility study are the following: (1) to provide a preliminary assessment of the feasibility of pumping semiconductor lasers in space directly focused sunlight; and (2) to identify semiconductor laser structures expected to operate at the lowest possible focusing intensities. It should be emphasized that the structures under consideration would provide direct optical-to-optical conversion of sunlight into laser light in a single crystal, in contrast to a configuration consisting of a solar cell or battery electrically pumping a current injection laser. With external modulation, such lasers may prove to be efficient sources for intersatellite communications. We proposed to develop a theoretical model of semiconductor quantum-well lasers photopumped by a broadband source, test it against existing experimental data where possible, and apply it to estimating solar pumping requirements and identifying optimum structures for operation for operation at low pump intensities. This report outlines our progress toward these goals. Discussion of several technical details are left to the attached summary abstract.

Antibody production using a ciliate generates unusual antibody glycoforms displaying enhanced cell-killing activity

PubMed Central

Calow, Jenny; Bockau, Ulrike; Struwe, Weston B.; Nowaczyk, Marc M.; Loser, Karin; Crispin, Max

2016-01-01

ABSTRACT Antibody glycosylation is a key parameter in the optimization of antibody therapeutics. Here, we describe the production of the anti-cancer monoclonal antibody rituximab in the unicellular ciliate, Tetrahymena thermophila. The resulting antibody demonstrated enhanced antibody-dependent cell-mediated cytotoxicity, which we attribute to unusual N-linked glycosylation. Detailed chromatographic and mass spectrometric analysis revealed afucosylated, oligomannose-type glycans, which, as a whole, displayed isomeric structures that deviate from the typical human counterparts, but whose branches were equivalent to fragments of metabolic intermediates observed in human glycoproteins. From the analysis of deposited crystal structures, we predict that the ciliate glycans adopt protein-carbohydrate interactions with the Fc domain that closely mimic those of native complex-type glycans. In addition, terminal glucose structures were identified that match biosynthetic precursors of human glycosylation. Our results suggest that ciliate-based expression systems offer a route to large-scale production of monoclonal antibodies exhibiting glycosylation that imparts enhanced cell killing activity. PMID:27594301

Magnetic and structural properties of yellow europium oxide compound and Eu(OH){sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Dongwook, E-mail: dongwookleedl324@gmail.com; Seo, Jiwon, E-mail: jiwonseo@yonsei.ac.kr; Valladares, Luis de los Santos

A new material based on a yellow europium oxide compound was prepared from europium oxide in a high vacuum environment. The structural and magnetic properties of the material were investigated. Owing to the absence of a crystal structure, the material exhibited a disordered magnetic behavior. In a reaction with deionized (DI) water without applied heat, the compound assumed a white color as soon as the DI water reached the powder, and the structure became polycrystalline Eu(OH){sub 3}. The magnetic properties, such as the thermal hysteresis, disappeared after the reaction with DI water, and the magnetic susceptibility of the yellow oxidemore » compound weakened. The magnetic properties of Eu(OH){sub 3} were also examined. Although Eu{sup 3+} is present in Eu(OH){sub 3}, a high magnetic moment due to the crystal field effect was observed. - Graphical abstract: (top left) Optical image of the yellow europium oxide compound. (top right) Optical image of the product of DI water and yellow europium oxide. (bottom) Magnetization curves as a function of temperature measured in various magnetic field. - Highlights: • We prepared a new material based on a yellow europium oxide compound from europium oxide. • We characterized the magnetic properties of the material which exhibits a disordered magnetic behavior such as thermal hysteresis. • The compound turned white (Eu(OH){sub 3}) as soon as the DI water reached the powder. • The thermal hysteresis disappeared after the reaction with DI water and the magnetic susceptibility of the yellow oxide compound weakened.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heffernan, Karina M.; Ross, Nancy L., E-mail: nross@vt.edu; Spencer, Elinor C.

Accurate elastic constants for gadolinium phosphate (GdPO{sub 4}) have been measured by single-crystal high-pressure diffraction methods. The bulk modulus of GdPO{sub 4} determined under hydrostatic conditions, 128.1(8) GPa (K′=5.8(2)), is markedly different from that obtained with GdPO{sub 4} under non-hydrostatic conditions (160(2) GPa), which indicates the importance of shear stresses on the elastic response of this phosphate. High pressure Raman and diffraction analysis indicate that the PO{sub 4} tetrahedra behave as rigid units in response to pressure and that contraction of the GdPO{sub 4} structure is facilitated by bending/twisting of the Gd–O–P links that result in increased distortion in themore » GdO{sub 9} polyhedra. - Graphical abstract: A high-pressure single crystal diffraction study of GdPO{sub 4} with the monazite structure is presented. The elastic behaviour of rare-earth phosphates are believed to be sensitive to shear forces. The bulk modulus of GdPO{sub 4} measured under hydrostatic conditions is 128.1(8) GPa. Compression of the structure is facilitated by bending/twisting of the Gd−O−P links that result in increased distortion in the GdO{sub 9} polyhedra. Display Omitted - Highlights: • The elastic responses of rare-earth phosphates are sensitive to shear forces. • The bulk modulus of GdPO{sub 4} measured under hydrostatic conditions is 128.1(8) GPa. • Twisting of the inter-polyhedral links allows compression of the GdPO{sub 4} structure. • Changes to the GdO{sub 9} polyhedra occur in response to pressure (<7.0 GPa).« less

Phenoxo bridged dinuclear Zn(II) Schiff base complex as new precursor for preparation zinc oxide nanoparticles: Synthesis, characterization, crystal structures and photoluminescence studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saeednia, S., E-mail: sami_saeednia@yahoo.com; Iranmanesh, P.; Ardakani, M. Hatefi

Highlights: • A novel nano-scale Zn(II) complex was synthesized by solvothermal method. • Chemical structure of the nanostructures was characterized as well as bulk complex. • The photoluminescence property of the complex was investigated at room temperature. • The thermogravimetry and differential thermal analysis were carried out. • Thermal decomposition of the nanostructures was prepared zinc oxide nanoparticles. - Abstract: Nanoparticles of a novel Zn(II) Schiff base complex, [Zn(HL)NO{sub 3}]{sub 2} (1), (H{sub 2}L = 2-[(2-hydroxy-propylimino) methyl] phenol), was synthesized by using solvothermal method. Shape, morphology and chemical structure of the synthesized nanoparticles were characterized by scanning electron microscopy (SEM),more » X-ray powder diffraction (XRD), Fourier Transform Infrared Spectoscopy (FT-IR) and UV–vis spectroscopy. Structural determination of compound 1 was determined by single-crystal X-ray diffraction. The results were revealed that the zinc complex is a centrosymmetric dimer in which deprotonated phenolates bridge the two five-coordinate metal atoms and link the two halves of the dimer. The thermal stability of compound 1 was analyzed by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect of the initial substrates concentration and reaction time on size and morphology of compound 1 nanostructure was investigated as well. Furthermore, the luminescent properties of the complex 1 were examined. ZnO nanoparticles with diameter between 15 and 20 nm were simply synthesized by solid-state transformation of compound 1 at 700 °C.« less

A top-down approach to crystal engineering of a racemic Δ2-isoxazoline.

PubMed

Lombardo, Giuseppe M; Rescifina, Antonio; Chiacchio, Ugo; Bacchi, Alessia; Punzo, Francesco

2014-02-01

The crystal structure of racemic dimethyl (4RS,5RS)-3-(4-nitrophenyl)-4,5-dihydroisoxazole-4,5-dicarboxylate, C13H12N2O7, has been determined by single-crystal X-ray diffraction. By analysing the degree of growth of the morphologically important crystal faces, a ranking of the most relevant non-covalent interactions determining the crystal structure can be inferred. The morphological information is considered with an approach opposite to the conventional one: instead of searching inside the structure for the potential key interactions and using them to calculate the crystal habit, the observed crystal morphology is used to define the preferential lines of growth of the crystal, and then this information is interpreted by means of density functional theory (DFT) calculations. Comparison with the X-ray structure confirms the validity of the strategy, thus suggesting this top-down approach to be a useful tool for crystal engineering.

Controlling ZIF-67 crystals formation through various cobalt sources in aqueous solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Xiangli; Jiangsu Key Laboratory of Advanced Metallic Materials, Nanjing 211189; Xing, Tiantian

2016-03-15

Zeolitic imidazolate frameworks ZIF-67 were prepared under hydrothermal (120 °C) and non-hydrothermal (room temperature) from various cobalt sources and 2-methylimidazolate (Hmim) in aqueous solution within 30 min. The particle size and morphology were found to be related to the reactivity of the cobalt salt, Hmim/Co{sup 2+} molar ratios and experimental condition. Using Co(NO{sub 3}){sub 2} as cobalt source, small-sized ZIF-67 crystals with agglomeration were formed. For CoCl{sub 2}, small-sized rhombic dodecahedron were obtained. While large-sized crystals of rhombic dodecahedron structure were obtained from CoSO{sub 4} and Co(OAc){sub 2}. Under hydrothermal condition, the size of ZIF-67 crystals tended to be moremore » uniform and the morphology were more regular comparing to non-hydrothermal condition. This study provides a simple way to control the size and morphology of ZIF-67 crystals prepared in aqueous solution. - Graphical abstract: Zeolitic imidazolate frameworks ZIF-67 were prepared under hydrothermal (120 °C) and non-hydrothermal (room temperature) from four different cobalt sources (Co(NO{sub 3}){sub 2}, CoCl{sub 2}, CoSO{sub 4} and Co(OAc){sub 2}) in aqueous solution within 30 min. The particle size and morphology were found to be related to the reactivity of the cobalt salt, Hmim/Co{sup 2+} molar ratios and experimental condition. - Highlights: • The particle size and morphology were determined by the reactivity of cobalt salt. • ZIF-67 could be prepared from CoSO{sub 4} and Co(OAc){sub 2} at Hmim/Co{sup 2+} molar ratio of 10. • Uniform and regular particles were obtained under hydrothermal condition.« less

Active site remodeling during the catalytic cycle in metal-dependent fructose-1,6-bisphosphate aldolases.

PubMed

Jacques, Benoit; Coinçon, Mathieu; Sygusch, Jurgen

2018-03-28

Crystal structures of two bacterial metal (Zn) dependent D-fructose 1,6-bisphosphate (FBP) aldolases in complex with substrate, analogues, and triose-P reaction products were determined to 1.5-2.0 Å resolution. The ligand complexes cryotrapped in native or mutant H. pylori aldolase crystals enabled a novel mechanistic description of FBP C 3 -C 4 bond cleavage. The reaction mechanism uses active site remodelling during the catalytic cycle implicating relocation of the Zn cofactor that is mediated by conformational changes of active site loops. Substrate binding initiates conformational changes, triggered upon P 1 -phosphate binding, which liberates the Zn chelating His180, allowing it to act as a general base for the proton abstraction at the FBP C 4 -hydroxyl group. A second zinc chelating His83 hydrogen bonds the substrate C 4 - hydroxyl group and assists cleavage by stabilizing the developing negative charge during proton abstraction. Cleavage is concerted with relocation of the metal cofactor from an interior to a surface exposed site, thereby stabilizing the nascent enediolate form. Conserved residue Glu142 is essential for protonation of the enediolate form, prior to product release. A D-tagatose 1,6-bisphosphate enzymatic complex reveals how His180 mediated proton abstraction controls stereospecificity of the cleavage reaction. Recognition and discrimination of the reaction products, dihydroxyacetone-P and D-glyceraldehyde-3-P, occurs via charged hydrogen bonds between hydroxyl groups of the triose-Ps and conserved residues, Asp82 and Asp255, respectively, and are crucial aspects of the enzyme's role in gluconeogenesis. Conformational changes in mobile loops β5-α7 and β6-α8 (containing catalytic residues Glu142 and His180, respectively) drive active site remodelling enabling the relocation of the metal cofactor. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

Crystal structure of the mutant D52S hen egg white lysozyme with an oligosaccharide product.

PubMed

Hadfield, A T; Harvey, D J; Archer, D B; MacKenzie, D A; Jeenes, D J; Radford, S E; Lowe, G; Dobson, C M; Johnson, L N

1994-11-11

The crystal structure of a mutant hen egg white lysozyme, in which the key catalytic residue aspartic acid 52 has been changed to a serine residue (D52S HEWL), has been determined and refined to a crystallographic R value of 0.173 for all data F > 0 between 8 and 1.9 A resolution. The D52S HEWL structure is very similar to the native HEWL structure (r.m.s. deviation of main-chain atoms 0.20 A). Small shifts that result from the change in hydrogen bonding pattern on substitution of Asp by Ser were observed in the loop between beta-strands in the region of residues 46 to 49. D52S HEWL exhibits less than 1% activity against the bacterial cell wall substrate. Cocrystallisation experiments with the hexasaccharide substrate beta(1-4) polymer of N-acetyl-D-glucosamine (GlcNAc6) resulted in crystals between 5 days and 14 days after the initial mixing of enzyme and substrate. Analysis by laser absorption mass spectrometry of the oligosaccharides present after incubation with native and D52S HEWL under conditions similar to those used for crystal growth showed that after 14 days with native HEWL complete catalysis to GlcNAc3. GlcNAc2 and GlcNac had occurred but with D52S HEWL only partial catalysis to the major products GlcNAc4 and GlcNAc2 had occurred and at least 50% of the GlcNAc6 remained intact. X-ray analysis of the D52S-oligosaccharide complex crystals showed that they contained the product GlcNAc4. The structure of the D52S HEWL-GlcNAc4 complex has been determined and refined to an R value of 0.160 for data between 8 and 2 A resolution. GlcNAc4 occupies sites A to D in the active site cleft. Careful refinement and examination of 2Fo-Fc electron density maps showed that the sugar in site D has the sofa conformation, a conformation previously observed with the HEWL complex with tetra-N-acetylglucosamine lactone transition state analogue, the HEWL complex with the cell wall trisaccharide and the phage T4 lysozyme complex with a cell wall product. The semi-axial C(5)-C(6) geometry of the sofa is stabilised by hydrogen bonds from the O-6 hydroxyl group to the main-chain N of Val109 and main-chain O of Ala107. The sugar in site D adopts the alpha configuration, seemingly in conflict with the observation that the hydrolysis of beta (1-4) glycosidie linkage by HEWL proceeds with 99.9% retention of beta-configuration.(ABSTRACT TRUNCATED AT 400 WORDS)

How disordered is my protein and what is its disorder for? A guide through the “dark side” of the protein universe

PubMed Central

Lieutaud, Philippe; Uversky, Alexey V.; Uversky, Vladimir N.; Longhi, Sonia

2016-01-01

ABSTRACT In the last 2 decades it has become increasingly evident that a large number of proteins are either fully or partially disordered. Intrinsically disordered proteins lack a stable 3D structure, are ubiquitous and fulfill essential biological functions. Their conformational heterogeneity is encoded in their amino acid sequences, thereby allowing intrinsically disordered proteins or regions to be recognized based on properties of these sequences. The identification of disordered regions facilitates the functional annotation of proteins and is instrumental for delineating boundaries of protein domains amenable to structural determination with X-ray crystallization. This article discusses a comprehensive selection of databases and methods currently employed to disseminate experimental and putative annotations of disorder, predict disorder and identify regions involved in induced folding. It also provides a set of detailed instructions that should be followed to perform computational analysis of disorder. PMID:28232901

Enhancement mechanism of field electron emission properties in hybrid carbon nanotubes with tree- and wing-like features

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, G.M.; School of Materials Science and Engineering, The University of New South Wales, NSW 2052; Yang, C.C., E-mail: ccyang@unsw.edu.a

2009-12-15

In this work, the tree-like carbon nanotubes (CNTs) with branches of different diameters and the wing-like CNTs with graphitic-sheets of different densities were synthesized by using plasma enhanced chemical vapor deposition. The nanostructures of the as-prepared hybrid carbon materials were characterized by scanning electron microscopy and transmission electron microscopy. The structural dependence of field electron emission (FEE) property was also investigated. It is found that both of the tree- and wing-like CNTs exhibit a lower turn-on field and higher emission current density than the pristine CNTs, which can be ascribed to the effects of branch size, crystal orientation, and graphitic-sheetmore » density. - Graphical abstract: Tree-like carbon nanotubes (CNTs) with branches and the wing-like CNTs with graphitic-sheets were synthesized by using plasma enhanced chemical vapor deposition. The structural dependence of field electron emission property was also investigated.« less

cis-trans Germanium chains in the intermetallic compounds ALi{sub 1-x}In{sub x}Ge{sub 2} and A{sub 2}(Li{sub 1-x}In{sub x}){sub 2}Ge{sub 3} (A=Sr, Ba, Eu)-experimental and theoretical studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

You, Tae-Soo; Bobev, Svilen, E-mail: bobev@udel.ed

Two types of strontium-, barium- and europium-containing germanides have been synthesized using high temperature reactions and characterized by single-crystal X-ray diffraction. All reported compounds also contain mixed-occupied Li and In atoms, resulting in quaternary phases with narrow homogeneity ranges. The first type comprises EuLi{sub 0.91(1)}In{sub 0.09}Ge{sub 2}, SrLi{sub 0.95(1)}In{sub 0.05}Ge{sub 2} and BaLi{sub 0.99(1)}In{sub 0.01}Ge{sub 2}, which crystallize in the orthorhombic space group Pnma (BaLi{sub 0.9}Mg{sub 0.1}Si{sub 2} structure type, Pearson code oP16). The lattice parameters are a=7.129(4)-7.405(4) A; b=4.426(3)-4.638(2) A; and c=11.462(7)-11.872(6) A. The second type includes Eu{sub 2}Li{sub 1.36(1)}In{sub 0.64}Ge{sub 3} and Sr{sub 2}Li{sub 1.45(1)}In{sub 0.55}Ge{sub 3}, whichmore » adopt the orthorhombic space group Cmcm (Ce{sub 2}Li{sub 2}Ge{sub 3} structure type, Pearson code oC28) with lattice parameters a=4.534(2)-4.618(2) A; b=19.347(8)-19.685(9) A; and c=7.164(3)-7.260(3) A. The polyanionic sub-structures in both cases feature one-dimensional Ge chains with alternating Ge-Ge bonds in cis- and trans-conformation. Theoretical studies using the tight-binding linear muffin-tin orbital (LMTO) method provide the rationale for optimizing the overall bonding by diminishing the {pi}-p delocalization along the Ge chains, accounting for the experimentally confirmed substitution of Li forIn. -- Graphical abstract: Presented are the single-crystal structures of two types of closely related intermetallics, as well as their band structures, calculated using tight-binding linear muffin-tin orbital (TB-LMTO-ASA) method. Display Omitted« less

Syntheses, crystal structures, and properties of four complexes based on polycarboxylate and imidazole ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiao, Rui; Chen, Shui-Sheng, E-mail: chenss@fync.edu.cn; Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093

2015-08-15

Four metal–organic coordination polymers [Zn(HL)(H{sub 2}O)]·4H{sub 2}O (1), [Zn(HL)(L{sub 1})]·4H{sub 2}O (2), [Cu(HL)(H{sub 2}O)]·3H{sub 2}O (3) and [Cu(HL)(L{sub 1})]·5H{sub 2}O (4) were synthesized by reactions of the corresponding metal(II) salts with semirigid polycarboxylate ligand (5-((4-carboxypiperidin-1-yl)methyl)isophthalic acid hydrochloride, H{sub 3}L·HCl) or auxiliary ligand (1,4-di(1H-imidazol-4-yl)benzene, L{sub 1}). The structures of the compounds were characterized by elemental analysis, FT-IR spectroscopy and single-crystal X-ray diffraction. The use of auxiliary ligand L{sub 1} has great influence on the structures of two pairs of complexes 1, 2 and 3, 4. Complex 1 is a uninodal 3-connected rare 2-fold interpenetrating ZnSc net with a Point (Schlafli) symbolmore » of (10{sup 3}) while 2 is a one-dimensional (1D) ladder structure. Compound 3 features a two-dimensional (2D) honeycomb network with typical 6{sup 3}-hcb topology, while 4 is 2D network with (4, 4) sql topology based on binuclear Cu{sup II} subunits. The non-covalent bonding interactions such as hydrogen bonds, π···π stacking and C–H···π exist in complexes 1–4, which contributes to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. And the photoluminescent property of 1 and 2 and gas sorption property of 4 have been investigated. - Graphical abstract: Four new coordination polymers have been obtained and their photoluminescent and gas sorption properties have also been investigated. - Highlights: • Two pairs of Zn{sup II}/ Cu{sup II} compounds have been synthesized. • Auxiliary ligand-controlled assembly of the complexes is reported. • The luminescent properties of complexes 1–2 were investigated. • The gas sorption property of 4 has been investigated.« less

Experimental and theoretical methods to study structural phase transition mechanisms in K{sub 3}WO{sub 3}F{sub 3} oxyfluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krylov, A.S., E-mail: shusy@iph.krasn.ru; Sofronova, S.N.; Kolesnikova, E.M.

2014-10-15

The results of structural phase transitions mechanisms study in K{sub 3}WO{sub 3}F{sub 3}oxyfluoride are represented by different experimental and theoretical methods. The structural phase transition anomalies at T{sub 1}=452 K and T{sub 2}=414 K of Raman and IR spectra have been analyzed. Using vibrational spectroscopy methods, the NMR-experiment has been done to clarify the nature of found phase transitions: displacive types or order-disorder types. The model of “disordered” crystal was proposed, and the results of lattice dynamics calculation in frameworks of the generalized Gordon–Kim method of ordered (R3) and “disordered” crystals were compared. The high pressure phases were studied bymore » the Raman technique too. - Graphical abstract: (1) Two possible configuration of octahedra. (2). All phases Raman lines of octahedra. (3) All phases IR lines of octahedra. (4) NMR spectra of all phases. - Highlights: • The results of study oxyfluoride K{sub 3}WO{sub 3}F{sub 3} are represented by Raman, IR, NMR technique. • The high pressure phases were studied by the Raman technique. • The anionic octahedra [WO{sub 3}F{sub 3}]{sup 3−} are not ordered below the both phase transitions. • The ferroelectric phase is realized due to the shift of atoms without F/O ordering. • Both of found phase transitions are close to the second order.« less

Nickel nanofibers synthesized by the electrospinning method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ji, Yi; Zhang, Xuebin, E-mail: zzhhxxbb@126.com; Zhu, Yajun

2013-07-15

Highlights: ► The nickel nanofibers have been obtained by electrospinning method. ► The nickel nanofibers had rough surface which was consisted of mass nanoparticles. ► The average diameter of nickel nanofibers is about 135 nm and high degree of crystallization. ► The Hc, Ms, and Mr were estimated to be 185 Oe, 51.9 and 16.9 emu/g respectively. - Abstract: In this paper, nickel nanofibers were prepared by electrospinning polyvinyl alcohol/nickel nitrate precursor solution followed by high temperature calcination in air and deoxidation in hydrogen atmosphere. The thermal stability of the as-electrospun PVA/Ni(NO{sub 3}){sub 2} composite nanofibers were characterized by TG–DSC.more » The morphologies and structures of the as-prepared samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field-emission scanning electronmicroscope (FE-SEM) and field-emission transmission electron microscopy (FE-TEM). The hysteresis loops (M–H loops) were measured by Physical Property Measurement System (PPMS). The results indicate that: the PVA and the nickel nitrate were almost completely decomposed at 460 °C and the products were pure nickel nanofibers with face-centered cubic (fcc) structure. Furthermore, the as-prepared nickel nanofibers had a continuous structure with rough surface and high degree of crystallization. The average diameter of nickel nanofibers was about 135 nm. The nanofibers showed a stronger coercivity of 185 Oe than value of bulk nickel.« less

Preparation of Gd(OH){sub 3} large single crystals by solid KOH assisted hydrothermal method and their luminescent and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Hai; Zhang, Youjin, E-mail: zyj@ustc.edu.cn; Zhou, Maozhong

Highlights: • Gd(OH){sub 3} large single crystals were prepared by solid KOH assisted hydrothermal method. • The possible growth mechanism of Gd(OH){sub 3} large single crystals was proposed. • The Gd(OH){sub 3} samples emitted a strong narrow-band ultraviolet B (NB-UVB) light. • The Gd(OH){sub 3} samples showed good paramagnetic properties. - Abstract: Large single crystals of gadolinium hydroxide [Gd(OH){sub 3}] in the length of several millimeters were successfully prepared by using solid KOH assisted hydrothermal method. Gd(OH){sub 3} samples were characterized by X-ray diffraction (XRD), 4-circle single-crystal diffraction, Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). FESEM imagemore » shows hexagonal prism morphology for the Gd(OH){sub 3} large crystals. The possible growth mechanism of Gd(OH){sub 3} large single crystals was proposed. The photoluminescence and magnetic properties of Gd(OH){sub 3} species were investigated.« less

Synthesis, crystal structures and optical properties of two congruent-melting isotypic diphosphates: LiM{sub 3}P{sub 2}O{sub 7} (M=Na, K)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi Yunjing; Wang Ying; Graduate University of the Chinese Academy of Sciences, Beijing 100039

2013-01-15

Two new isotypic diphosphates, LiNa{sub 3}P{sub 2}O{sub 7} (1) and LiK{sub 3}P{sub 2}O{sub 7} (2), have been synthesized by conventional solid-state reaction. The single-crystal X-ray structural analyses have shown that they crystallize in the orthorhombic space group C222{sub 1} (No. 20) with the unit cells: a=5.4966(2) A, b=9.1365(4) A, c=12.2764(5) A for compound 1 and a=6.0373(14) A, b=9.339(2) A, c=13.292(3) A for compound 2. The LiM{sub 3}P{sub 2}O{sub 7} (M=Na, K) consist of two-dimensional [LiP{sub 2}O{sub 7}]{sup 3-} layers, which are composed by LiO{sub 4} tetrahedral and diphosphate groups, the Na or K atoms are filled in the interlayers andmore » balance the charge. Second harmonic generation (SHG) on powder samples have been measured using Kurtz and Perry techniques. Thermal analyses, IR spectroscopy, UV-vis-NIR diffuse reflectance spectra, and band structure calculations are performed on the reported compounds. - Graphical Abstract: LiM{sub 3}P{sub 2}O{sub 7} (M=Na, K) consists of a two-dimensional infinite [LiP{sub 2}O{sub 7}]{sup 3-} layer, which is composed by LiO{sub 4} tetrahedra and diphosphate groups. Highlights: Black-Right-Pointing-Pointer LiNa{sub 3}P{sub 2}O{sub 7} and LiK{sub 3}P{sub 2}O{sub 7} are new compounds in the Li{sub 2}O-M{sub 2}O (M=Na, K)-P{sub 2}O{sub 5} systems. Black-Right-Pointing-Pointer Crystal structures of LiNa{sub 3}P{sub 2}O{sub 7} and LiK{sub 3}P{sub 2}O{sub 7} consist of two-dimensional [LiP{sub 2}O{sub 7}]{sup 3-} layers. Black-Right-Pointing-Pointer LiNa{sub 3}P{sub 2}O{sub 7} and LiK{sub 3}P{sub 2}O{sub 7} are congruent melting compounds.« less

Structure–property relations of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}·2H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haussühl, Eiken, E-mail: haussuehl@kristall.uni-frankfurt.de; Schreuer, Jürgen; Wiehl, Leonore

2014-04-01

Large single crystals of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}·2H{sub 2}O with dimensions up to 40×40×30 mm{sup 3} were grown from aqueous solutions. The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies and their shifts upon variation of pressure, respectively, using the plate-resonance technique. Additionally, the coefficients of thermal expansion were determined between 95 K and 305 K by dilatometry. The elastic behaviour at ambient conditions is dominated by the 2-dimensional network of strong hydrogen bonds within the (001) plane leading to a corresponding pseudo-tetragonal anisotropy of the longitudinal elastic stiffness. The variation of elastic propertiesmore » with pressure, however, as well as the thermal expansion shows strong deviations from the pseudo-tetragonal symmetry. These deviations are probably correlated with tilts of the elongated tri-nuclear betaine–CuCl{sub 2}–water complexes. Neither the thermal expansion nor the specific heat capacity gives any hint on a phase transition in the investigated temperature range. - Graphical abstract: Single crystal of orthorhombic [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}·2H{sub 2}O. - Highlights: • Large single crystals (40 ×40 ×30 mm{sup 3}) of [(CH{sub 3}){sub 3}NCH{sub 2}COO]{sub 2}(CuCl{sub 2}){sub 3}·2H{sub 2}O were grown. • The elastic and piezoelastic coefficients were derived from ultrasonic resonance frequencies. • Thermal expansion (95 K–305 K) and heat capacity (113 K–323 K) were determined. • The orthorhombic structure shows pseudo-tetragonal elastic anisotropy at ambient conditions. • The crystal structure is stable in the investigated range (1–1600 bar, 95–303 K)« less

Syntheses and characterization of elpasolite-type ammonium alkali metal hexafluorometallates(III)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mi Jinxiao; Key Laboratory of New Processing Technology for Nonferrous Metals and Materials; Luo Shuming

Crystal structures of three fluorides (NH{sub 4}){sub 2}NaFeF{sub 6}, (Fe), (NH{sub 4}){sub 2}NaGaF{sub 6}, (Ga), and (NH{sub 4}){sub 2}NaCrF{sub 6}, (Cr), as well as a substituted compound [(NH{sub 4}){sub 1-x}K{sub x}]{sub 2}KAlF{sub 6} (x{approx}0.17), (Al), have been refined using single-crystal and powder X-ray diffraction techniques. All these four ammonium hexafluorides have a cubic elpasolite-type structure and crystallize in the space group Fm3-bar m with lattice constants a=8.483(3), 8.450 (3), 8.4472(2) and 8.724(3) A for compounds (Fe), (Ga), (Cr) and (Al), respectively. The effective ionic radius of the ammonium ion calculated from those compounds has a mean value of R=1.729 Amore » for CN=12. An ultraviolet-visible absorption spectrum of (NH{sub 4}){sub 2}NaCrF{sub 6}, measured at room temperature, gives a crystal field (Dq=1575 cm{sup -1}) and Racah parameters (B=758 cm{sup -1} and C=3374 cm{sup -1}). Abnormal anisotropic thermal parameters of fluorine atoms have been observed in the compound (Al), and interpreted to arise from four strong hydrogen bonds (F...H-N) that are distributed in a square form around each fluorine atom. - Graphical abstract: Abnormal anisotropic thermal parameters of fluorine atoms have been observed in the compound [(NH{sub 4}){sub 1-x}K{sub x}]{sub 2}KAlF{sub 6} (x{approx}0.17), and interpreted to arise from four strong hydrogen bonds (F...H-N) that are distributed in a square form around each fluorine atom. The endmembers' phase transitions at low temperature are believed to be caused by them.« less

Salvage of failed protein targets by reductive alkylation.

PubMed

Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

2014-01-01

The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins.

Salvage of Failed Protein Targets by Reductive Alkylation

PubMed Central

Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

2014-01-01

The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins. PMID:24590719

Extending the applicability of the Goldschmidt tolerance factor to arbitrary ionic compounds

PubMed Central

Sato, Toyoto; Takagi, Shigeyuki; Deledda, Stefano; Hauback, Bjørn C.; Orimo, Shin-ichi

2016-01-01

Crystal structure determination is essential for characterizing materials and their properties, and can be facilitated by various tools and indicators. For instance, the Goldschmidt tolerance factor (T) for perovskite compounds is acknowledged for evaluating crystal structures in terms of the ionic packing. However, its applicability is limited to perovskite compounds. Here, we report on extending the applicability of T to ionic compounds with arbitrary ionic arrangements and compositions. By focussing on the occupancy of constituent spherical ions in the crystal structure, we define the ionic filling fraction (IFF), which is obtained from the volumes of crystal structure and constituent ions. Ionic compounds, including perovskites, are arranged linearly by the IFF, providing consistent results with T. The linearity guides towards finding suitable unit cell and composition, thus tackling the main obstacle for determining new crystal structures. We demonstrate the utility of the IFF by solving the structure of three hydrides with new crystal structures. PMID:27032978

Extending the applicability of the Goldschmidt tolerance factor to arbitrary ionic compounds.

PubMed

Sato, Toyoto; Takagi, Shigeyuki; Deledda, Stefano; Hauback, Bjørn C; Orimo, Shin-ichi

2016-04-01

Crystal structure determination is essential for characterizing materials and their properties, and can be facilitated by various tools and indicators. For instance, the Goldschmidt tolerance factor (T) for perovskite compounds is acknowledged for evaluating crystal structures in terms of the ionic packing. However, its applicability is limited to perovskite compounds. Here, we report on extending the applicability of T to ionic compounds with arbitrary ionic arrangements and compositions. By focussing on the occupancy of constituent spherical ions in the crystal structure, we define the ionic filling fraction (IFF), which is obtained from the volumes of crystal structure and constituent ions. Ionic compounds, including perovskites, are arranged linearly by the IFF, providing consistent results with T. The linearity guides towards finding suitable unit cell and composition, thus tackling the main obstacle for determining new crystal structures. We demonstrate the utility of the IFF by solving the structure of three hydrides with new crystal structures.

Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beheshti, Azizolla, E-mail: a.beheshti@scu.ac.ir; Nozarian, Kimia; Babadi, Susan Soleymani

Two new compounds namely [Cu(SCN)(µ-L)]{sub n} (1) and ([Ag (µ{sub 2}-L)](ClO{sub 4})){sub n} (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS{sub 2}N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, themore » adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS{sub 4} tetrahedral geometry with 4-membered Ag{sub 2}S{sub 2} rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV–vis spectrum could be attributed to the π→π* and MLCT transitions, respectively. - Graphical abstract: Two new Cu(I) and Ag(I) coordination polymers have been have been synthesized by one-pot reactions. Copper complex has a 2D non-covalent structure, but silver compound is a 3D coordination compound. These compounds have effective antibacterial activity. - Highlights: • Cu(I) and Ag(I) based coordination polymers have different network structures. • Ag(I) polymer has more antibacterial activity than Cu(I) polymer. • DFT calculations of Cu(I) polymer has been investigated. • Cu(I) and Ag(I) polymers can destroy the structure of chromosomal and plasmid DNA.« less

From screen to structure with a harvestable microfluidic device.

PubMed

Stojanoff, Vivian; Jakoncic, Jean; Oren, Deena A; Nagarajan, V; Poulsen, Jens-Christian Navarro; Adams-Cioaba, Melanie A; Bergfors, Terese; Sommer, Morten O A

2011-08-01

Advances in automation have facilitated the widespread adoption of high-throughput vapour-diffusion methods for initial crystallization screening. However, for many proteins, screening thousands of crystallization conditions fails to yield crystals of sufficient quality for structural characterization. Here, the rates of crystal identification for thaumatin, catalase and myoglobin using microfluidic Crystal Former devices and sitting-drop vapour-diffusion plates are compared. It is shown that the Crystal Former results in a greater number of identified initial crystallization conditions compared with vapour diffusion. Furthermore, crystals of thaumatin and lysozyme obtained in the Crystal Former were used directly for structure determination both in situ and upon harvesting and cryocooling. On the basis of these results, a crystallization strategy is proposed that uses multiple methods with distinct kinetic trajectories through the protein phase diagram to increase the output of crystallization pipelines.

Synthesis and structures of ligand-dominated one-dimensional silver(I)–bis(pyridylmethyl)amine coordination chains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Hung-Jui; Liu, Yu-Chiao; Tseng, Yu-Jui

2016-10-15

Reactants slow diffusion of Ag(I) salts with 3,4′-bis(pyridylmethyl)amine (3,4′-bpma), an unsymmetric bis-pyridyl ligand equipped with a non-innocent amine backbone, afforded polymeric coordination adducts 1–5 having a general formula ([Ag(3,4′-bpma)(solv)]X){sub n} (solv = H{sub 2}O, CH{sub 3}OH, and none; X= CF{sub 3}CO{sub 2}{sup –}, BF{sub 4}{sup –}, ClO{sub 4}{sup –}, CF{sub 3}SO{sub 3}{sup –}, and SbF{sub 6}{sup –}). Single-crystal X-ray diffraction (SCXRD) analyses reveal that colorless crystals of Ag(I) coordination polymers (CPs) 1–5 have very similar one-dimensional (1D) non-flat chain structures, which are preferentially depicted as a “zipper-like” rather than a ladder-like or a double-stranded chain topologies. The 3,4′-bpma ligand inmore » these Ag(I) CPs displays a μ{sub 3}-bridging mode with a gauche–trans (1,4, and 5) and a trans–trans (2 and 3) conformations. Noteworthy, anions do not show strong influence on structural modulation of Ag(I) CPs in the solid state, but really affect CP conformations and packing fashions, indicative of a ligand-dominated assembly process for such a Ag(I)–3,4′-bpma system. Thermal stabilities and solid-state photoluminescence properties of crystalline materials 1–5 were investigated. - Graphical abstract: This work has addressed five ligand-dominated Ag(I)–3,4′-bpma polymeric adducts, which show similar one-dimensional non-flat chain structures depicting a “zipper-like” topology rather than a ladder-like or a double-stranded chain structures.« less

M(II)-dipyridylamide-based coordination frameworks (M=Mn, Co, Ni): Structural transformation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tzeng, Biing-Chiau; Selvam, TamilSelvi; Tsai, Miao-Hsin

2016-11-15

A series of 1-D double-zigzag (([M(papx){sub 2}(H{sub 2}O){sub 2}](ClO{sub 4}){sub 2}){sub n}; M=Mn, x=s (1), x=o (3); M=Co, x=s (4), x=o (5); M=Ni, x=s (6), x=o (7)) and 2-D polyrotaxane ([Mn(paps){sub 2}(ClO{sub 4}){sub 2}]{sub n} (2)) frameworks were synthesized by reactions of M(ClO{sub 4}){sub 2} (M=Mn, Co, and Ni) with papx (paps, N,N’-bis(pyridylcarbonyl)-4,4’-diaminodiphenylthioether; papo, N,N’-bis(pyridylcarbonyl)-4,4’-diaminodiphenyl ether), which have been isolated and structurally characterized by X-ray diffraction. Based on powder X-ray diffraction (PXRD) experiments, heating the double-zigzag frameworks underwent structural transformation to give the respective polyrotaxane ones. Moreover, grinding the solid samples of the respective polyrotaxanes in the presence of moisturemore » also resulted in the total conversion to the original double-zigzag frameworks. In this study, we have successfully extended studies to Mn{sup II}, Co{sup II}, and Ni{sup II} frameworks from the previous Zn{sup II}, Cd{sup II}, and Cu{sup II} ones, and interestingly such structural transformation is able to be proven experimentally by powder and single-crystal X-ray diffraction studies as well. - Graphical abstract: 1-D double-zigzag and 2-D polyrotaxane frameworks of M(II)-papx (x=s, o; M=Mn, Co, Ni) frameworks can be interconverted by heating and grinding in the presence of moiture, and such structural transformation has be proven experimentally by powder and single-crystal X-ray diffraction studies.« less

The crystal structure of the bifunctional deaminase/reductase RibD of the riboflavin biosynthetic pathway in Escherichia coli: implications for the reductive mechanism.

PubMed

Stenmark, Pål; Moche, Martin; Gurmu, Daniel; Nordlund, Pär

2007-10-12

We have determined the crystal structure of the bi-functional deaminase/reductase enzyme from Escherichia coli (EcRibD) that catalyzes two consecutive reactions during riboflavin biosynthesis. The polypeptide chain of EcRibD is folded into two domains where the 3D structure of the N-terminal domain (1-145) is similar to cytosine deaminase and the C-terminal domain (146-367) is similar to dihydrofolate reductase. We showed that EcRibD is dimeric and compared our structure to tetrameric RibG, an ortholog from Bacillus subtilis (BsRibG). We have also determined the structure of EcRibD in two binary complexes with the oxidized cofactor (NADP(+)) and with the substrate analogue ribose-5-phosphate (RP5) and superposed these two in order to mimic the ternary complex. Based on this superposition we propose that the invariant Asp200 initiates the reductive reaction by abstracting a proton from the bound substrate and that the pro-R proton from C4 of the cofactor is transferred to C1 of the substrate. A highly flexible loop is found in the reductase active site (159-173) that appears to control cofactor and substrate binding to the reductase active site and was therefore compared to the corresponding Met20 loop of E. coli dihydrofolate reductase (EcDHFR). Lys152, identified by comparing substrate analogue (RP5) coordination in the reductase active site of EcRibD with the homologous reductase from Methanocaldococcus jannaschii (MjaRED), is invariant among bacterial RibD enzymes and could contribute to the various pathways taken during riboflavin biosynthesis in bacteria and yeast.

Structural and optical properties of WTe2 single crystals synthesized by DVT technique

NASA Astrophysics Data System (ADS)

Dixit, Vijay; Vyas, Chirag; Pathak, V. M.; Soalanki, G. K.; Patel, K. D.

2018-05-01

Layered transition metal di-chalcogenide (LTMDCs) crystals have attracted much attention due to their potential in optoelectronic device applications recently due to realization of their monolayer based structures. In the present investigation we report growth of WTe2 single crystals by direct vapor transport (DVT) technique. These crystals are then characterized by energy dispersive analysis of x-rays (EDAX) to study stoichiometric composition after growth. The structural properties are studied by x-ray diffraction (XRD) and selected area electron diffraction (SAED) is used to confirm orthorhombic structure of grown WTe2 crystal. Surface morphological properties of the crystals are also studied by scanning electron microscope (SEM). The optical properties of the grown crystals are studied by UV-Visible spectroscopy which gives direct band gap of 1.44 eV for grown WTe2 single crystals.

Solvent effects on the crystal growth structure and morphology of the pharmaceutical dirithromycin

NASA Astrophysics Data System (ADS)

Wang, Yuan; Liang, Zuozhong

2017-12-01

Solvent effects on the crystal structure and morphology of pharmaceutical dirithromycin molecules were systematically investigated using both experimental crystallization and theoretical simulation. Dirithromycin is one of the new generation of macrolide antibiotics with two polymorphic forms (Form I and Form II) and many solvate forms. Herein, six solvates of the dirithromycin, including acetonitrile, acetonitrile/water, acetone, 1-propanol, N,N-dimethylformamide (DMF) and cyclohexane, were studied. Experimentally, we crystallized the dirithromycin molecules in different solvents by the solvent evaporating method and measured the crystal structures with the X-ray diffraction (XRD). We compared these crystal structures of dirithromycin solvates and analyzed the solvent property-determined structure evolution. The solvents have a strong interaction with the dirithromycin molecule due to the formation of inter-molecular interactions (such as the hydrogen bonding and close contacts (sum of vdW radii)). Theoretically, we calculated the ideal crystal habit based on the solvated structures with the attachment growth (AE) model. The predicted morphologies and aspect ratios of dirithromycin solvates agree well with the experimental results. This work could be helpful to better understand the structure and morphology evolution of solvates controlled by solvents and guide the crystallization of active pharmaceutical ingredients in the pharmaceutical industry.

Molecular Dynamic Simulation of Space and Earth-Grown Crystal Structures of Thermostable T1 Lipase Geobacillus zalihae Revealed a Better Structure.

PubMed

Ishak, Siti Nor Hasmah; Aris, Sayangku Nor Ariati Mohamad; Halim, Khairul Bariyyah Abd; Ali, Mohd Shukuri Mohamad; Leow, Thean Chor; Kamarudin, Nor Hafizah Ahmad; Masomian, Malihe; Rahman, Raja Noor Zaliha Raja Abd

2017-09-25

Less sedimentation and convection in a microgravity environment has become a well-suited condition for growing high quality protein crystals. Thermostable T1 lipase derived from bacterium Geobacillus zalihae has been crystallized using the counter diffusion method under space and earth conditions. Preliminary study using YASARA molecular modeling structure program for both structures showed differences in number of hydrogen bond, ionic interaction, and conformation. The space-grown crystal structure contains more hydrogen bonds as compared with the earth-grown crystal structure. A molecular dynamics simulation study was used to provide insight on the fluctuations and conformational changes of both T1 lipase structures. The analysis of root mean square deviation (RMSD), radius of gyration, and root mean square fluctuation (RMSF) showed that space-grown structure is more stable than the earth-grown structure. Space-structure also showed more hydrogen bonds and ion interactions compared to the earth-grown structure. Further analysis also revealed that the space-grown structure has long-lived interactions, hence it is considered as the more stable structure. This study provides the conformational dynamics of T1 lipase crystal structure grown in space and earth condition.

Synthesis, crystal structures, and physical properties of the new Zintl phases A{sub 21}Zn{sub 4}Pn{sub 18} (A=Ca, Eu; Pn=As, Sb)—Versatile arrangements of [ZnPn{sub 4}] tetrahedra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suen, Nian-Tzu; Wang, Yi; Bobev, Svilen, E-mail: bobev@udel.edu

Four new Zintl phases, Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18} and Eu{sub 21}Zn{sub 4}Sb{sub 18} have been synthesized by metal flux reactions. Their structures have been established from single-crystal X-ray diffraction. Despite the similar chemical makeup and the identical formulae, the structures of the four compounds are not the same—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18} and Eu{sub 21}Zn{sub 4}As{sub 18} crystallize in the monoclinic space group C2/m (No. 12, Z=4) with the β-Ca{sub 21}Mn{sub 4}Sb{sub 18} structure type, while Eu{sub 21}Zn{sub 4}Sb{sub 18} adopts the Ba{sub 21}Cd{sub 4}Sb{sub 18} structure type withmore » the orthorhombic space group Cmce (No. 64, Z=8). Both structures are based on ZnAs{sub 4} or ZnSb{sub 4} tetrahedra, linked in slightly different ways, and Ca{sup 2+} and Eu{sup 2+} cations that fill the space between them. The structural relationships between the title compounds and other known ternary phases with intricate structures are discussed. Electrical resistivity measurement on single-crystalline Eu{sub 21}Zn{sub 4}Sb{sub 18} suggests an intrinsic semiconductor behavior with a band gap of ca. 0.2 eV. The temperature dependent DC magnetization measurement on the same material indicates Curie–Weiss paramagnetism in the high-temperature regime, and a spontaneous antiferromagnetic ordering below 8 K. The calculated effective moments of Eu confirm the divalent Eu{sup 2+} ground state, as expected from the Zintl–Klemm concept. - Graphical abstract: The four new Zintl phases—Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18}—crystallize in two structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. - Highlights: • Ca{sub 21}Zn{sub 4}As{sub 18}, Ca{sub 21}Zn{sub 4}Sb{sub 18}, Eu{sub 21}Zn{sub 4}As{sub 18}, and Eu{sub 21}Zn{sub 4}Sb{sub 18} are new compounds in the respective ternary phase diagrams. • They form with structure types, showing the versatility in the arrangements of ZnAs{sub 4} and ZnSb{sub 4} tetrahedra. • For both structures, the valence electron count follows the Zintl–Klemm rules.« less

Use of Crystal Structure Informatics for Defining the Conformational Space Needed for Predicting Crystal Structures of Pharmaceutical Molecules.

PubMed

Iuzzolino, Luca; Reilly, Anthony M; McCabe, Patrick; Price, Sarah L

2017-10-10

Determining the range of conformations that a flexible pharmaceutical-like molecule could plausibly adopt in a crystal structure is a key to successful crystal structure prediction (CSP) studies. We aim to use conformational information from the crystal structures in the Cambridge Structural Database (CSD) to facilitate this task. The conformations produced by the CSD Conformer Generator are reduced in number by considering the underlying rotamer distributions, an analysis of changes in molecular shape, and a minimal number of molecular ab initio calculations. This method is tested for five pharmaceutical-like molecules where an extensive CSP study has already been performed. The CSD informatics-derived set of crystal structure searches generates almost all the low-energy crystal structures previously found, including all experimental structures. The workflow effectively combines information on individual torsion angles and then eliminates the combinations that are too high in energy to be found in the solid state, reducing the resources needed to cover the solid-state conformational space of a molecule. This provides insights into how the low-energy solid-state and isolated-molecule conformations are related to the properties of the individual flexible torsion angles.

Two distinct crystallization processes in supercooled liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tane, Masakazu, E-mail: mtane@sanken.osaka-u.ac.jp; Kimizuka, Hajime; Ichitsubo, Tetsu

2016-05-21

Using molecular dynamics simulations we show that two distinct crystallization processes, depending on the temperature at which crystallization occurs, appear in a supercooled liquid. As a model for glass-forming materials, an Al{sub 2}O{sub 3} model system, in which both the glass transition and crystallization from the supercooled liquid can be well reproduced, is employed. Simulations in the framework of an isothermal-isobaric ensemble indicate that the calculated time-temperature-transformation curve for the crystallization to γ(defect spinel)-Al{sub 2}O{sub 3} exhibited a typical nose shape, as experimentally observed in various glass materials. During annealing above the nose temperature, the structure of the supercooled liquidmore » does not change before the crystallization, because of the high atomic mobility (material transport). Thus, the crystallization is governed by the abrupt crystal nucleation, which results in the formation of a stable crystal structure. In contrast, during annealing below the nose temperature, the structure of the supercooled liquid gradually changes before the crystallization, and the formed crystal structure is less stable than that formed above the nose temperature, because of the restricted material transport.« less

Correlation of Intermolecular Acyl Transfer Reactivity with Noncovalent Lattice Interactions in Molecular Crystals: Toward Prediction of Reactivity of Organic Molecules in the Solid State.

PubMed

Krishnaswamy, Shobhana; Shashidhar, Mysore S

2018-04-06

Intermolecular acyl transfer reactivity in several molecular crystals was studied, and the outcome of the reactivity was analyzed in the light of structural information obtained from the crystals of the reactants. Minor changes in the molecular structure resulted in significant variations in the noncovalent interactions and packing of molecules in the crystal lattice, which drastically affected the facility of the intermolecular acyl transfer reactivity in these crystals. Analysis of the reactivity vs crystal structure data revealed dependence of the reactivity on electrophile···nucleophile interactions and C-H···π interactions between the reacting molecules. The presence of these noncovalent interactions augmented the acyl transfer reactivity, while their absence hindered the reactivity of the molecules in the crystal. The validity of these correlations allows the prediction of intermolecular acyl transfer reactivity in crystals and co-crystals of unknown reactivity. This crystal structure-reactivity correlation parallels the molecular structure-reactivity correlation in solution-state reactions, widely accepted as organic functional group transformations, and sets the stage for the development of a similar approach for reactions in the solid state.

Prediction and theoretical characterization of p-type organic semiconductor crystals for field-effect transistor applications.

PubMed

Atahan-Evrenk, Sule; Aspuru-Guzik, Alán

2014-01-01

The theoretical prediction and characterization of the solid-state structure of organic semiconductors has tremendous potential for the discovery of new high performance materials. To date, the theoretical analysis mostly relied on the availability of crystal structures obtained through X-ray diffraction. However, the theoretical prediction of the crystal structures of organic semiconductor molecules remains a challenge. This review highlights some of the recent advances in the determination of structure-property relationships of the known organic semiconductor single-crystals and summarizes a few available studies on the prediction of the crystal structures of p-type organic semiconductors for transistor applications.

The potential for the indirect crystal structure verification of methyl glycosides based on acetates' parent structures: GIPAW and solid-state NMR approaches

NASA Astrophysics Data System (ADS)

Szeleszczuk, Łukasz; Gubica, Tomasz; Zimniak, Andrzej; Pisklak, Dariusz M.; Dąbrowska, Kinga; Cyrański, Michał K.; Kańska, Marianna

2017-10-01

A convenient method for the indirect crystal structure verification of methyl glycosides was demonstrated. Single-crystal X-ray diffraction structures for methyl glycoside acetates were deacetylated and subsequently subjected to DFT calculations under periodic boundary conditions. Solid-state NMR spectroscopy served as a guide for calculations. A high level of accuracy of the modelled crystal structures of methyl glycosides was confirmed by comparison with published results of neutron diffraction study using RMSD method.

Synthesis, structure and DFT conformation analysis of CpNiX(NHC) and NiX2(NHC)2 (X = SPh or Br) complexes

NASA Astrophysics Data System (ADS)

Malan, Frederick P.; Singleton, Eric; van Rooyen, Petrus H.; Conradie, Jeanet; Landman, Marilé

2017-11-01

The synthesis, density functional theory (DFT) conformational study and structure analysis of novel two-legged piano stool Ni N-heterocyclic carbene (NHC) complexes and square planar Ni bis-N-heterocyclic carbene complexes, all containing either bromido- or thiophenolato ligands, are described. [CpNi(SPh)(NHC)] complexes were obtained from the neutral 18-electron [CpNiBr(NHC)] complexes by substitution of a bromido ligand with SPh, using NEt3 as a base to abstract the proton of HSPh. The 16-electron biscarbene complexes [Ni(SPh)2{NHC}2] were isolated when an excess of HSPh was added to the reaction mixture. Biscarbene complexes of the type [NiBr2(NHC)2] were obtained in the reaction of NiCp2 with a slight excess of the specific imidazolium bromide salt. The molecular and electronic structures of the mono- and bis-N-heterocyclic carbene complexes have been analysed using single crystal diffraction and density functional theory (DFT) calculations, to give insight into their structural properties.

Structural properties of a family of hydrogen-bonded co-crystals formed between gemfibrozil and hydroxy derivatives of t-butylamine, determined directly from powder X-ray diffraction data

NASA Astrophysics Data System (ADS)

Cheung, Eugene Y.; David, Sarah E.; Harris, Kenneth D. M.; Conway, Barbara R.; Timmins, Peter

2007-03-01

We report the formation and structural properties of co-crystals containing gemfibrozil and hydroxy derivatives of t-butylamine H 2NC(CH 3) 3-n(CH 2OH) n, with n=0, 1, 2 and 3. In each case, a 1:1 co-crystal is formed, with transfer of a proton from the carboxylic acid group of gemfibrozil to the amino group of the t-butylamine derivative. All of the co-crystal materials prepared are polycrystalline powders, and do not contain single crystals of suitable size and/or quality for single crystal X-ray diffraction studies. Structure determination of these materials has been carried out directly from powder X-ray diffraction data, using the direct-space Genetic Algorithm technique for structure solution followed by Rietveld refinement. The structural chemistry of this series of co-crystal materials reveals well-defined structural trends within the first three members of the family ( n=0, 1, 2), but significantly contrasting structural properties for the member with n=3.

In-situ study on growth units of Ba2Mg(B3O6)2 crystal

NASA Astrophysics Data System (ADS)

Lv, X. S.; Sun, Y. L.; Tang, X. L.; Wan, S. M.; Zhang, Q. L.; You, J. L.; Yin, S. T.

2013-05-01

BMBO (Ba2Mg(B3O6)2 crystal) is an excellent birefringent crystal and a potential stimulated Raman scattering (SRS) crystal. In this paper, high temperature Raman spectroscopy was used to in-situ study the melt structure near a BMBO crystal-melt interface. [B3O6]3- groups were found in this region. The result reveals that both of BaO bonds and MgO bonds are the weak bonds in the BMBO crystal structure. During the melting process, the crystal structure broke into Ba2+ ions, Mg2+ ions and [B3O6]3- groups. Our experimental results confirmed that the well-developed faces of BMBO crystals are the (001), (101) and (012) faces. Based on attachment energy theory, the crystal growth habit was discussed. The (001) (101) and (012) crystal faces linked by the weak BaO bonds and MgO bonds have smaller attachment energies and slower growth rates, and thus present in the final morphology. The (012) crystal face has a multi-terrace structure, which suggests that BMBO crystal grows with a layer-by-layer mode.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meng, Jiang Ping; Yan, Zhi Shuo; Long, Ji Ying

By using a rigid dicarboxylate ligand, 4,5-di(4′-carboxylphenyl)benzene (H{sub 2}L), two complexes formulated as SrL(DMF)(H{sub 2}O)·(CH{sub 3}CN) (DMF=N,N′-dimethylformamide) (1) and BaL(H{sub 2}O){sub 2} (2) were solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1 and 2 display two-dimensional (2D) layer structures. The two complexes exhibit different electrochemical and photoelectrochemical properties. Their thermal stabilities, cyclic voltammograms, UV–vis absorption and diffuse reflectance spectra and photoluminescence properties have been investigated. The band structures, the total density of states (TDOS) and partial density of states (PDOS) of the two complexes were calculated by CASTEP program. Complex 2 exhibits much higher photocurrent density thanmore » complex 1. The Mott–Schottky plots reveal that complexes 1 and 2 both are p-type semiconductors, which are in agreement with their band structure calculations. - Graphical abstract: Two alkaline earth metal(II) complexes with 2D layer structures are p-type semiconductors, they possess different band structures and density of states. And the Ba(II) complex 2 exhibits much higher photocurrent density than the Sr(II) complex 1.« less

Centrosymmetry vs noncentrosymmetry in La{sub 2}Ga{sub 0.33}SbS{sub 5} and Ce{sub 4}GaSbS{sub 9} based on the interesting size effects of lanthanides: Syntheses, crystal structures, and optical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Hua-Jun, E-mail: cszzl772002@yeah.net; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

Two new quaternary sulfides La{sub 2}Ga{sub 0.33}SbS{sub 5} and Ce{sub 4}GaSbS{sub 9} have been prepared from stoichiometric elements at 1223 K in an evacuated silica tube. Interestingly, La{sub 2}Ga{sub 0.33}SbS{sub 5} crystallizes in the centrosymmetric structure, while Ce{sub 4}GaSbS{sub 9} crystallizes in the noncentrosymmetric structure, which show obvious size effects of lanthanides on the crystal structures of these two compounds. Ce{sub 4}GaSbS{sub 9} belongs to RE{sub 4}GaSbS{sub 9} (RE=Pr, Nd, Sm, Gd–Ho) structure type with a=13.8834(9) Å, b=14.3004(11) Å, c=14.4102(13) Å, V=2861.0(4) Å{sup 3}. The structure features infinite chains of [Ga{sub 2}Sb{sub 2}S{sub 11}{sup 10–}]{sub ∞} propagating along a directionmore » separated by Ce{sup 3+} cations and S{sup 2−} anions. La{sub 2}Ga{sub 0.33}SbS{sub 5} adopts the family of La{sub 4}FeSb{sub 2}S{sub 10}-related structure with a=7.5193(6) Å, c=13.4126(17) Å, V=758.35(13) Å{sup 3}. Its structure is built up from the alternate stacking of La/Sb/S and La/Ga/S 2D building blocks. The La/Sb/S slabs consist of teeter-totter chains of Sb1S{sub 4} seesaws, which are connected via sharing the apexes of μ{sub 4}-S1. Moreover, La1 is positionally disordered with Sb1 and stabilized in a bicapped trigonal prismatic coordination sphere. Between these La/Sb/S slabs, La2S{sub 8} square antiprisms are connected via edge-sharing into 2D building blocks, creating tetrahedral sites partially occupied by the Ga1 atoms. UV/Vis diffuse reflectance spectroscopy study shows that the optical gap of La{sub 2}Ga{sub 0.33}SbS{sub 5} is about 1.76 eV. - Graphical abstract: Two new quaternary sulfides La{sub 2}Ga{sub 0.33}SbS{sub 5} and Ce{sub 4}GaSbS{sub 9} have been prepared by solid-state reactions. Ce{sub 4}GaSbS{sub 9} crystallizes in RE{sub 4}GaSbS{sub 9} (RE=Pr, Nd, Sm, Gd–Ho) structure type, while La{sub 2}Ga{sub 0.33}SbS{sub 5} belongs to the family of La{sub 4}FeSb{sub 2}S{sub 10}-related structure and exhibits an optical gap of 1.76 eV. - Highlights: • Two new quaternary sulfides La{sub 2}Ga{sub 0.33}SbS{sub 5} and Ce{sub 4}GaSbS{sub 9} have been prepared by solid-state reaction. • Ce{sub 4}GaSbS{sub 9} crystallizes in RE{sub 4}GaSbS{sub 9} (RE=Pr, Nd, Sm, Gd–Ho) structure type, while La{sub 2}Ga{sub 0.33}SbS{sub 5} belongs to the family of La{sub 4}FeSb{sub 2}S{sub 10}-related structure. • The optical gap of 1.76 eV for La{sub 2}Ga{sub 0.33}SbS{sub 5} was deduced from UV/Vis reflectance spectroscopy.« less

Structural analysis of β-glucosidase mutants derived from a hyperthermophilic tetrameric structure

PubMed Central

Nakabayashi, Makoto; Kataoka, Misumi; Mishima, Yumiko; Maeno, Yuka; Ishikawa, Kazuhiko

2014-01-01

β-Glucosidase from Pyrococcus furiosus (BGLPf) is a hyperthermophilic tetrameric enzyme which can degrade cellooligosaccharides to glucose under hyperthermophilic conditions and thus holds promise for the saccharification of lignocellulosic biomass at high temperature. Prior to the production of large amounts of this enzyme, detailed information regarding the oligomeric structure of the enzyme is required. Several crystals of BGLPf have been prepared over the past ten years, but its crystal structure had not been solved until recently. In 2011, the first crystal structure of BGLPf was solved and a model was constructed at somewhat low resolution (2.35 Å). In order to obtain more detailed structural data on BGLPf, the relationship between its tetrameric structure and the quality of the crystal was re-examined. A dimeric form of BGLPf was constructed and its crystal structure was solved at a resolution of 1.70 Å using protein-engineering methods. Furthermore, using the high-resolution crystal structural data for the dimeric form, a monomeric form of BGLPf was constructed which retained the intrinsic activity of the tetrameric form. The thermostability of BGLPf is affected by its oligomeric structure. Here, the biophysical and biochemical properties of engineered dimeric and monomeric BGLPfs are reported, which are promising prototype models to apply to the saccharification reaction. Furthermore, details regarding the oligomeric structures of BGLPf and the reasons why the mutations yielded improved crystal structures are discussed. PMID:24598756

Structure of β-AgGaO{sub 2}; ternary I–III–VI{sub 2} oxide semiconductor with a wurtzite-derived structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagatani, Hiraku; Suzuki, Issei; Kita, Masao

2015-02-15

The structure of the wurtzite-derived β-AgGaO{sub 2} was refined by Rietveld analysis of high-resolution powder diffraction data obtained using synchrotron X-ray radiation. The space group of the crystal is Pna2{sub 1} with lattice parameters of a{sub 0}=5.56175 Å, b{sub 0}=7.14749 Å, and c{sub 0}=5.46875 Å. The deviation of O–Ag–O and M–O–M bond angles from the regular tetrahedral angle of 109.5° was very large at ∼8° and ∼11°, respectively. The electronic structure of β-AgGaO{sub 2} is discussed based on its structure, and the indirect band gap of β-AgGaO{sub 2} was related to significant tetrahedral distortion. Although β-AgGaO{sub 2} decomposes into metallicmore » silver and Ga{sub 2}O{sub 3} at a high temperature in any atmosphere, β-AgGaO{sub 2} is stable up to 690 °C under an O{sub 2} atmosphere. No direct transformation from the wurtzite-derived phase to a delafossite phase occurs in β-AgGaO{sub 2}. - Graphical abstract: Crystal structure of β-AgGaO{sub 2} was refined by Rietveld analysis. AgO{sub 4} and O(Ag,Ga){sub 4} tetrahedra are significantly distorted from ideal tetrahedron. - Highlights: • Orthorhombic β-AgGaO{sub 2} with a wurtzite-derived β-NaFeO{sub 2} structure was synthesized. • Its structure was refined by Rietveld analysis of high-resolution XRD data. • Silver and oxygen tetrahedra are significantly distorted from an ideal tetrahedron. • The extent of this tetrahedral distortion is related to the band gap nature. • β-AgGaO{sub 2} is a metastable phase but is stable up to 690 °C in an O{sub 2} atmosphere.« less

Crystal structures and magnetic properties of two-dimensional antiferromagnets Co{sub 1-x}Zn{sub x}TeMoO{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doi, Yoshihiro, E-mail: doi@sci.hokudai.ac.j; Suzuki, Ryo; Hinatsu, Yukio

2009-12-15

Crystal structures and magnetic properties of metal telluromolybdates Co{sub 1-x}Zn{sub x}TeMoO{sub 6} (x=0.0, 0.1,...,0.9) are reported. All the compounds have an orthorhombic structure with space group P2{sub 1}2{sub 1}2 and a charge configuration of M{sup 2+}Te{sup 4+}Mo{sup 6+}O{sub 6}. In this structure, M ions form a pseudo-two-dimensional lattice in the ab plane. Their magnetic susceptibility measurements have been performed in the temperature range between 1.8 and 300 K. The end member CoTeMoO{sub 6} shows a magnetic transition at 24.4 K. The transition temperature for solid solutions rapidly decreases with increasing x and this transition disappears between x=0.4 and 0.5, whichmore » is corresponding to the percolation limit for the square-planer lattice. From the magnetization, specific heat, and powder neutron diffraction measurements, it is found that the magnetic transition observed in the CoTeMoO{sub 6} is a canted antiferromagnetic ordering of Co{sup 2+} ions. The antiferromagnetic component of the ordered magnetic moment (3.12(3)mu{sub B} at 10 K) is along the b-axis. In addition, there exists a small ferromagnetic component (0.28(3)mu{sub B}) along the a-axis. - Graphical abstract: The metal telluromolybdates Co{sub 1-x}Zn{sub x}TeMoO{sub 6} have an orthorhombic structure with space group P2{sub 1}2{sub 1}2. In this structure, M ions form a pseudo-square-planer lattice in the ab plane. These compounds show a low-dimensional magnetism reflecting this structural feature. The magnetic transition observed in the CoTeMoO{sub 6} is a canted antiferromagnetic ordering of Co{sup 2+} ions, and the figure is the magnetic structure.« less

Structural Insight into How Bacteria Prevent Interference between Multiple Divergent Type IV Secretion Systems

PubMed Central

Phan, Isabelle Q. H.; Scheib, Holger; Subramanian, Sandhya; Edwards, Thomas E.; Lehman, Stephanie S.; Piitulainen, Hanna; Sayeedur Rahman, M.; Rennoll-Bankert, Kristen E.; Staker, Bart L.; Taira, Suvi; Stacy, Robin; Myler, Peter J.; Azad, Abdu F.

2015-01-01

ABSTRACT Prokaryotes use type IV secretion systems (T4SSs) to translocate substrates (e.g., nucleoprotein, DNA, and protein) and/or elaborate surface structures (i.e., pili or adhesins). Bacterial genomes may encode multiple T4SSs, e.g., there are three functionally divergent T4SSs in some Bartonella species (vir, vbh, and trw). In a unique case, most rickettsial species encode a T4SS (rvh) enriched with gene duplication. Within single genomes, the evolutionary and functional implications of cross-system interchangeability of analogous T4SS protein components remains poorly understood. To lend insight into cross-system interchangeability, we analyzed the VirB8 family of T4SS channel proteins. Crystal structures of three VirB8 and two TrwG Bartonella proteins revealed highly conserved C-terminal periplasmic domain folds and dimerization interfaces, despite tremendous sequence divergence. This implies remarkable structural constraints for VirB8 components in the assembly of a functional T4SS. VirB8/TrwG heterodimers, determined via bacterial two-hybrid assays and molecular modeling, indicate that differential expression of trw and vir systems is the likely barrier to VirB8-TrwG interchangeability. We also determined the crystal structure of Rickettsia typhi RvhB8-II and modeled its coexpressed divergent paralog RvhB8-I. Remarkably, while RvhB8-I dimerizes and is structurally similar to other VirB8 proteins, the RvhB8-II dimer interface deviates substantially from other VirB8 structures, potentially preventing RvhB8-I/RvhB8-II heterodimerization. For the rvh T4SS, the evolution of divergent VirB8 paralogs implies a functional diversification that is unknown in other T4SSs. Collectively, our data identify two different constraints (spatiotemporal for Bartonella trw and vir T4SSs and structural for rvh T4SSs) that mediate the functionality of multiple divergent T4SSs within a single bacterium. PMID:26646013

Synchrotron X-ray diffraction and Raman spectroscopy of Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm-Lu) ceramics obtained by molten-salt synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siqueira, K.P.F.; Soares, J.C.; Granado, E.

2014-01-15

Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) ceramics were obtained by molten-salt synthesis and their structures were systematically investigated by synchrotron X-ray diffraction (SXRD), second harmonic generation (SHG) and Raman spectroscopy. It was observed that ceramics with the largest ionic radii (La, Pr, Nd) crystallized into the Pmcn space group, while the ceramics with intermediate ionic radii (Sm-Gd) exhibited a different crystal structure belonging to the Ccmm space group. For this last group of ceramics, this result was corroborated by SHG and Raman scattering and ruled out any possibility formore » the non-centrosymmetric C 222{sub 1} space group, solving a recent controversy in the literature. Finally, according to SXRD, Tb-Lu containing samples exhibited an average defect fluorite structure (Fm3{sup ¯}m space group). Nonetheless, broad scattering at forbidden Bragg reflections indicates the presence of short-range domains with lower symmetry. Vibrational spectroscopy showed the presence of six Raman-active modes, inconsistent with the average cubic fluorite structure, and in line with the existence of lower-symmetry nano-domains immersed in the average fluorite structure of these ceramics. - Graphical abstract: Raman spectrum for Sm{sub 3}NbO{sub 7} ceramics showing their 27 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. Display Omitted - Highlights: • Ln{sub 3}NbO{sub 7} ceramics were obtained by molten-salt synthesis. • SXRD, SHG and Raman scattering confirmed orthorhombic and cubic structures. • Ccmm instead of C222{sub 1} is the correct structure for Sm–Gd ceramics. • Pmcn space group was confirmed for La-, Pr- and Nd-based ceramics. • For Tb–Lu ceramics, ordered domains of a pyrochlore structure were observed.« less

Bimetallic iron and cobalt incorporated MFI/MCM-41 composite and its catalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Baoshan, E-mail: bsli@mail.buct.edu.cn; Xu, Junqing; Li, Xiao

2012-05-15

Graphical abstract: The formation of FeCo-MFI/MCM-41 composite is based on two steps, the first step of synthesizing the MFI-type proto-zeolite unites under hydrothermal conditions. The second step of assembling these zeolite fragment together new silica and heteroatom source on the CTAB surfactant micelle to synthesize the mesoporous product with hexagonal structure. Highlights: Black-Right-Pointing-Pointer Bimetallic iron and cobalt incorporated MFI/MCM-41 composite was prepared using templating method. Black-Right-Pointing-Pointer FeCo-MFI/MCM-41 composite simultaneously possessed two kinds of meso- and micro-porous structures. Black-Right-Pointing-Pointer Iron and cobalt ions incorporated into the silica framework with tetrahedral coordination. -- Abstract: The MFI/MCM-41 composite material with bimetallic Fe andmore » Co incorporation was prepared using templating method via a two-step hydrothermal crystallization procedure. The obtained products were characterized by a series of techniques including powder X-ray diffraction, N{sub 2} sorption, transmission electron microscopy, scanning electron microscope, H{sub 2} temperature programmed reduction, thermal analyses, and X-ray absorption fine structure spectroscopy of the Fe and Co K-edge. The catalytic properties of the products were investigated by residual oil hydrocracking reactions. Characterization results showed that the FeCo-MFI/MCM-41 composite simultaneously possessed two kinds of stable meso- and micro-porous structures. Iron and cobalt ions were incorporated into the silicon framework, which was confirmed by H{sub 2} temperature programmed reduction and X-ray absorption fine structure spectroscopy. This composite presented excellent activities in hydrocracking of residual oil, which was superior to the pure materials of silicate-1/MCM-41.« less

Optical properties of transparent glass–ceramics containing lithium–mica nanocrystals: Crystallization effect

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khani, V.; Alizadeh, P., E-mail: p-alizadeh@modares.ac.ir; Shakeri, M.S.

2013-09-01

Graphical abstract: Optical properties of transparent Li{sub 2}O–MgO–Al{sub 2}O{sub 3}–SiO{sub 2}–F glasses containing lithium–mica nanocrystals are studied and crystallization condition has been evaluated and optimized to produce transparent glass–ceramics. Crystallization temperatures were determined by differential thermal analysis and crystalline phases were identified and quantified by X-ray diffraction. Scanning electron microscopy was used for morphological variations and UV–vis absorption spectroscopy for comparative analysis of transparency. In order to investigate the optical properties of transparent glass–ceramics, optical band gap, Fermi energy level and Urbach energy are calculated. The results of the investigation illustrate that band gap is reduced with increases in crystallizationmore » time and temperature. Enhanced orderliness in the arrangement of atoms might be regarded as possible reasons for the above changes. - Highlights: • The optimum temperature and time of crystallization were determined. • Li–mica nanocrystals with size of <30 nm were formed using a two-step heat-treatment. • Optical band gap and Fermi energy of nanocrystalline materials decreased with increasing of crystallization temperature and time. • Urbach band tailing was decreased with increasing of crystallization condition. - Abstract: Optical properties of transparent Li{sub 2}O–MgO–Al{sub 2}O{sub 3}–SiO{sub 2}–F glasses containing lithium–mica nanocrystals were studied. The crystallization condition of these glasses was evaluated and optimized to produce transparent glass–ceramics. Crystallization temperatures were determined by differential thermal analysis and crystalline phases were identified and quantified by X-ray diffraction. Scanning electron microscopy was used to detect morphological changes and UV–vis absorption spectroscopy was used for comparative analysis of transparency. In order to investigate the optical properties of the transparent glass–ceramics, optical band gap, Fermi energy level and Urbach energy were calculated. The results of the investigation illustrate that the band gap is reduced with increases in crystallization time and temperature. Enhanced orderliness in the arrangement of atoms might be regarded as possible reasons for the above changes.« less

Multiple solvent crystal structures of ribonuclease A: An assessment of the method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dechene, Michelle; Wink, Glenna; Smith, Mychal

2010-11-12

The multiple solvent crystal structures (MSCS) method uses organic solvents to map the surfaces of proteins. It identifies binding sites and allows for a more thorough examination of protein plasticity and hydration than could be achieved by a single structure. The crystal structures of bovine pancreatic ribonuclease A (RNAse A) soaked in the following organic solvents are presented: 50% dioxane, 50% dimethylformamide, 70% dimethylsulfoxide, 70% 1,6-hexanediol, 70% isopropanol, 50% R,S,R-bisfuran alcohol, 70% t-butanol, 50% trifluoroethanol, or 1.0M trimethylamine-N-oxide. This set of structures is compared with four sets of crystal structures of RNAse A from the protein data bank (PDB) andmore » with the solution NMR structure to assess the validity of previously untested assumptions associated with MSCS analysis. Plasticity from MSCS is the same as from PDB structures obtained in the same crystal form and deviates only at crystal contacts when compared to structures from a diverse set of crystal environments. Furthermore, there is a good correlation between plasticity as observed by MSCS and the dynamic regions seen by NMR. Conserved water binding sites are identified by MSCS to be those that are conserved in the sets of structures taken from the PDB. Comparison of the MSCS structures with inhibitor-bound crystal structures of RNAse A reveals that the organic solvent molecules identify key interactions made by inhibitor molecules, highlighting ligand binding hot-spots in the active site. The present work firmly establishes the relevance of information obtained by MSCS.« less

A hybrid phononic crystal for roof application.

PubMed

Wan, Qingmian; Shao, Rong

2017-11-01

Phononic crystal is a type of acoustic material, and the study of phononic crystals has attracted great attention from national research institutions. Meanwhile, noise reduction in the low-frequency range has always encountered difficulties and troubles in the engineering field. In order to obtain a unique and effective low-frequency noise reduction method, in this paper a low frequency noise attenuation system based on phononic crystal structure is proposed and demonstrated. The finite element simulation of the band gap is consistent with the final test results. The effects of structure parameters on the band gaps were studied by changing the structure parameters and the band gaps can be controlled by suitably tuning structure parameters. The structure and results provide a good support for phononic crystal structures engineering application.

Crystallized N-terminal domain of influenza virus matrix protein M1 and method of determining and using same

NASA Technical Reports Server (NTRS)

Luo, Ming (Inventor); Sha, Bingdong (Inventor)

2000-01-01

The matrix protein, M1, of influenza virus strain A/PR/8/34 has been purified from virions and crystallized. The crystals consist of a stable fragment (18 Kd) of the M1 protein. X-ray diffraction studies indicated that the crystals have a space group of P3.sub.t 21 or P3.sub.2 21. Vm calculations showed that there are two monomers in an asymmetric unit. A crystallized N-terminal domain of M1, wherein the N-terminal domain of M1 is crystallized such that the three dimensional structure of the crystallized N-terminal domain of M1 can be determined to a resolution of about 2.1 .ANG. or better, and wherein the three dimensional structure of the uncrystallized N-terminal domain of M1 cannot be determined to a resolution of about 2.1 .ANG. or better. A method of purifying M1 and a method of crystallizing M1. A method of using the three-dimensional crystal structure of M1 to screen for antiviral, influenza virus treating or preventing compounds. A method of using the three-dimensional crystal structure of M1 to screen for improved binding to or inhibition of influenza virus M1. The use of the three-dimensional crystal structure of the M1 protein of influenza virus in the manufacture of an inhibitor of influenza virus M1. The use of the three-dimensional crystal structure of the M1 protein of influenza virus in the screening of candidates for inhibition of influenza virus M1.

X-ray laser diffraction for structure determination of the rhodopsin-arrestin complex

NASA Astrophysics Data System (ADS)

Zhou, X. Edward; Gao, Xiang; Barty, Anton; Kang, Yanyong; He, Yuanzheng; Liu, Wei; Ishchenko, Andrii; White, Thomas A.; Yefanov, Oleksandr; Han, Gye Won; Xu, Qingping; de Waal, Parker W.; Suino-Powell, Kelly M.; Boutet, Sébastien; Williams, Garth J.; Wang, Meitian; Li, Dianfan; Caffrey, Martin; Chapman, Henry N.; Spence, John C. H.; Fromme, Petra; Weierstall, Uwe; Stevens, Raymond C.; Cherezov, Vadim; Melcher, Karsten; Xu, H. Eric

2016-04-01

Serial femtosecond X-ray crystallography (SFX) using an X-ray free electron laser (XFEL) is a recent advancement in structural biology for solving crystal structures of challenging membrane proteins, including G-protein coupled receptors (GPCRs), which often only produce microcrystals. An XFEL delivers highly intense X-ray pulses of femtosecond duration short enough to enable the collection of single diffraction images before significant radiation damage to crystals sets in. Here we report the deposition of the XFEL data and provide further details on crystallization, XFEL data collection and analysis, structure determination, and the validation of the structural model. The rhodopsin-arrestin crystal structure solved with SFX represents the first near-atomic resolution structure of a GPCR-arrestin complex, provides structural insights into understanding of arrestin-mediated GPCR signaling, and demonstrates the great potential of this SFX-XFEL technology for accelerating crystal structure determination of challenging proteins and protein complexes.

X-ray laser diffraction for structure determination of the rhodopsin-arrestin complex.

PubMed

Zhou, X Edward; Gao, Xiang; Barty, Anton; Kang, Yanyong; He, Yuanzheng; Liu, Wei; Ishchenko, Andrii; White, Thomas A; Yefanov, Oleksandr; Han, Gye Won; Xu, Qingping; de Waal, Parker W; Suino-Powell, Kelly M; Boutet, Sébastien; Williams, Garth J; Wang, Meitian; Li, Dianfan; Caffrey, Martin; Chapman, Henry N; Spence, John C H; Fromme, Petra; Weierstall, Uwe; Stevens, Raymond C; Cherezov, Vadim; Melcher, Karsten; Xu, H Eric

2016-04-12

Serial femtosecond X-ray crystallography (SFX) using an X-ray free electron laser (XFEL) is a recent advancement in structural biology for solving crystal structures of challenging membrane proteins, including G-protein coupled receptors (GPCRs), which often only produce microcrystals. An XFEL delivers highly intense X-ray pulses of femtosecond duration short enough to enable the collection of single diffraction images before significant radiation damage to crystals sets in. Here we report the deposition of the XFEL data and provide further details on crystallization, XFEL data collection and analysis, structure determination, and the validation of the structural model. The rhodopsin-arrestin crystal structure solved with SFX represents the first near-atomic resolution structure of a GPCR-arrestin complex, provides structural insights into understanding of arrestin-mediated GPCR signaling, and demonstrates the great potential of this SFX-XFEL technology for accelerating crystal structure determination of challenging proteins and protein complexes.

X-ray laser diffraction for structure determination of the rhodopsin-arrestin complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, X. Edward; Gao, Xiang; Barty, Anton

Here, serial femtosecond X-ray crystallography (SFX) using an X-ray free electron laser (XFEL) is a recent advancement in structural biology for solving crystal structures of challenging membrane proteins, including G-protein coupled receptors (GPCRs), which often only produce microcrystals. An XFEL delivers highly intense X-ray pulses of femtosecond duration short enough to enable the collection of single diffraction images before significant radiation damage to crystals sets in. Here we report the deposition of the XFEL data and provide further details on crystallization, XFEL data collection and analysis, structure determination, and the validation of the structural model. The rhodopsin-arrestin crystal structure solvedmore » with SFX represents the first near-atomic resolution structure of a GPCR-arrestin complex, provides structural insights into understanding of arrestin-mediated GPCR signaling, and demonstrates the great potential of this SFX-XFEL technology for accelerating crystal structure determination of challenging proteins and protein complexes.« less

X-ray laser diffraction for structure determination of the rhodopsin-arrestin complex

PubMed Central

Zhou, X. Edward; Gao, Xiang; Barty, Anton; Kang, Yanyong; He, Yuanzheng; Liu, Wei; Ishchenko, Andrii; White, Thomas A.; Yefanov, Oleksandr; Han, Gye Won; Xu, Qingping; de Waal, Parker W.; Suino-Powell, Kelly M.; Boutet, Sébastien; Williams, Garth J.; Wang, Meitian; Li, Dianfan; Caffrey, Martin; Chapman, Henry N.; Spence, John C.H.; Fromme, Petra; Weierstall, Uwe; Stevens, Raymond C.; Cherezov, Vadim; Melcher, Karsten; Xu, H. Eric

2016-01-01

Serial femtosecond X-ray crystallography (SFX) using an X-ray free electron laser (XFEL) is a recent advancement in structural biology for solving crystal structures of challenging membrane proteins, including G-protein coupled receptors (GPCRs), which often only produce microcrystals. An XFEL delivers highly intense X-ray pulses of femtosecond duration short enough to enable the collection of single diffraction images before significant radiation damage to crystals sets in. Here we report the deposition of the XFEL data and provide further details on crystallization, XFEL data collection and analysis, structure determination, and the validation of the structural model. The rhodopsin-arrestin crystal structure solved with SFX represents the first near-atomic resolution structure of a GPCR-arrestin complex, provides structural insights into understanding of arrestin-mediated GPCR signaling, and demonstrates the great potential of this SFX-XFEL technology for accelerating crystal structure determination of challenging proteins and protein complexes. PMID:27070998

X-ray laser diffraction for structure determination of the rhodopsin-arrestin complex

DOE PAGES

Zhou, X. Edward; Gao, Xiang; Barty, Anton; ...

2016-04-12

Here, serial femtosecond X-ray crystallography (SFX) using an X-ray free electron laser (XFEL) is a recent advancement in structural biology for solving crystal structures of challenging membrane proteins, including G-protein coupled receptors (GPCRs), which often only produce microcrystals. An XFEL delivers highly intense X-ray pulses of femtosecond duration short enough to enable the collection of single diffraction images before significant radiation damage to crystals sets in. Here we report the deposition of the XFEL data and provide further details on crystallization, XFEL data collection and analysis, structure determination, and the validation of the structural model. The rhodopsin-arrestin crystal structure solvedmore » with SFX represents the first near-atomic resolution structure of a GPCR-arrestin complex, provides structural insights into understanding of arrestin-mediated GPCR signaling, and demonstrates the great potential of this SFX-XFEL technology for accelerating crystal structure determination of challenging proteins and protein complexes.« less

Crystal growth, differential gas adsorption, high thermal stability, and reversible coordination of two new barium-organic frameworks, Ba(SBA)(DMF){sub 4} and Ba{sub 2}(BTEC)(H{sub 2}O)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halake, Shobha; Ok, Kang Min, E-mail: kmok@cau.ac.kr

2015-11-15

Single crystals of two barium-organic framework materials, Ba(SBA)(DMF){sub 4} (CAUMOF-15) and Ba{sub 2}(BTEC)(H{sub 2}O) (CAUMOF-16), have been grown through solvothermal reactions (H{sub 2}SBA=4,4′-sulfonyldibenzoic acid and H{sub 4}BTEC=1,2,4,5-benzenetetracarboxylic acid). The crystal structures of the reported frameworks have been determined by single-crystal X-ray diffraction. The materials have been fully characterized by powder X-ray diffraction (PXRD), elemental analyses, Infrared (IR) spectroscopy, and thermogravimetric analyses (TGA). CAUMOF-15 reveals a three-dimensional open-framework that comprises of an inorganic motif with one-dimensional chains and the SBA linkers. CAUMOF-16 shows another three-dimensional backbone consisting of layers of edge-shared BaO{sub 9} and BaO{sub 10} polyhedra, and BTEC pillars. Bothmore » of the 3D frameworks exhibit relatively high thermal stabilities. The PXRD and IR spectral data confirm that CAUMOF-15 and CAUMOF-16 reveal reversible coordinations of the respective solvent molecules, DMF and H{sub 2}O. Gas adsorption properties towards nitrogen, hydrogen, and carbon dioxide have been also investigated. - Graphical abstract: Crystals of two new barium-organic frameworks, Ba(SBA)(DMF){sub 4} and Ba{sub 2}(BTEC)(H{sub 2}O), exhibiting a differential gas adsorption, a high thermal stability, and a reversible coordination of solvent molecules have been grown. - Highlights: • Crystals of two new 3D Ba-MOFs are grown. • The two Ba-MOFs reveal very high thermal stabilities up to ca. 400 °C. • Ba(SBA)(DMF){sub 4} exhibits differential gas adsorption properties. • The two Ba-MOFs show reversible coordination of the solvent molecules.« less

Growth and dislocation studies of β-HMX.

PubMed

Gallagher, Hugh G; Sherwood, John N; Vrcelj, Ranko M

2014-01-01

The defect structure of organic materials is important as it plays a major role in their crystal growth properties. It also can play a subcritical role in "hot-spot" detonation processes of energetics and one such energetic is cyclotetramethylene-tetranitramine, in the commonly used beta form (β-HMX). The as-grown crystals grown by evaporation from acetone show prismatic, tabular and columnar habits, all with {011}, {110}, (010) and (101) faces. Etching on (010) surfaces revealed three different types of etch pits, two of which could be identified with either pure screw or pure edge dislocations, the third is shown to be an artifact of the twinning process that this material undergoes. Examination of the {011} and {110} surfaces show only one type of etch pit on each surface; however their natural asymmetry precludes the easy identification of their Burgers vector or dislocation type. Etching of cleaved {011} surfaces demonstrates that the etch pits can be associated with line dislocations. All dislocations appear randomly on the crystal surfaces and do not form alignments characteristic of mechanical deformation by dislocation slip. Crystals of β-HMX grown from acetone show good morphological agreement with that predicted by modelling, with three distinct crystal habits observed depending upon the supersaturation of the growth solution. Prismatic habit was favoured at low supersaturation, while tabular and columnar crystals were predominant at higher super saturations. The twin plane in β-HMX was identified as a (101) reflection plane. The low plasticity of β-HMX is shown by the lack of etch pit alignments corresponding to mechanically induced dislocation arrays. On untwinned {010} faces, two types of dislocations exist, pure edge dislocations with b = [010] and pure screw dislocations with b = [010]. On twinned (010) faces, a third dislocation type exists and it is proposed that these pits are associated with pure screw dislocations with b = [010]. Graphical abstractEtch pits on the twinned (010) face of β-HMX.

Statistical Analysis of Crystallization Database Links Protein Physico-Chemical Features with Crystallization Mechanisms

PubMed Central

Fusco, Diana; Barnum, Timothy J.; Bruno, Andrew E.; Luft, Joseph R.; Snell, Edward H.; Mukherjee, Sayan; Charbonneau, Patrick

2014-01-01

X-ray crystallography is the predominant method for obtaining atomic-scale information about biological macromolecules. Despite the success of the technique, obtaining well diffracting crystals still critically limits going from protein to structure. In practice, the crystallization process proceeds through knowledge-informed empiricism. Better physico-chemical understanding remains elusive because of the large number of variables involved, hence little guidance is available to systematically identify solution conditions that promote crystallization. To help determine relationships between macromolecular properties and their crystallization propensity, we have trained statistical models on samples for 182 proteins supplied by the Northeast Structural Genomics consortium. Gaussian processes, which capture trends beyond the reach of linear statistical models, distinguish between two main physico-chemical mechanisms driving crystallization. One is characterized by low levels of side chain entropy and has been extensively reported in the literature. The other identifies specific electrostatic interactions not previously described in the crystallization context. Because evidence for two distinct mechanisms can be gleaned both from crystal contacts and from solution conditions leading to successful crystallization, the model offers future avenues for optimizing crystallization screens based on partial structural information. The availability of crystallization data coupled with structural outcomes analyzed through state-of-the-art statistical models may thus guide macromolecular crystallization toward a more rational basis. PMID:24988076

Statistical analysis of crystallization database links protein physico-chemical features with crystallization mechanisms.

PubMed

Fusco, Diana; Barnum, Timothy J; Bruno, Andrew E; Luft, Joseph R; Snell, Edward H; Mukherjee, Sayan; Charbonneau, Patrick

2014-01-01

X-ray crystallography is the predominant method for obtaining atomic-scale information about biological macromolecules. Despite the success of the technique, obtaining well diffracting crystals still critically limits going from protein to structure. In practice, the crystallization process proceeds through knowledge-informed empiricism. Better physico-chemical understanding remains elusive because of the large number of variables involved, hence little guidance is available to systematically identify solution conditions that promote crystallization. To help determine relationships between macromolecular properties and their crystallization propensity, we have trained statistical models on samples for 182 proteins supplied by the Northeast Structural Genomics consortium. Gaussian processes, which capture trends beyond the reach of linear statistical models, distinguish between two main physico-chemical mechanisms driving crystallization. One is characterized by low levels of side chain entropy and has been extensively reported in the literature. The other identifies specific electrostatic interactions not previously described in the crystallization context. Because evidence for two distinct mechanisms can be gleaned both from crystal contacts and from solution conditions leading to successful crystallization, the model offers future avenues for optimizing crystallization screens based on partial structural information. The availability of crystallization data coupled with structural outcomes analyzed through state-of-the-art statistical models may thus guide macromolecular crystallization toward a more rational basis.

Eukaryotic major facilitator superfamily transporter modeling based on the prokaryotic GlpT crystal structure.

PubMed

Lemieux, M Joanne

2007-01-01

The major facilitator superfamily (MFS) of transporters represents the largest family of secondary active transporters and has a diverse range of substrates. With structural information for four MFS transporters, we can see a strong structural commonality suggesting, as predicted, a common architecture for MFS transporters. The rate for crystal structure determination of MFS transporters is slow, making modeling of both prokaryotic and eukaryotic transporters more enticing. In this review, models of eukaryotic transporters Glut1, G6PT, OCT1, OCT2 and Pho84, based on the crystal structures of the prokaryotic GlpT, based on the crystal structure of LacY are discussed. The techniques used to generate the different models are compared. In addition, the validity of these models and the strategy of using prokaryotic crystal structures to model eukaryotic proteins are discussed. For comparison, E. coli GlpT was modeled based on the E. coli LacY structure and compared to the crystal structure of GlpT demonstrating that experimental evidence is essential for accurate modeling of membrane proteins.

The use of small-molecule structures to complement protein–ligand crystal structures in drug discovery

PubMed Central

Cole, Jason C.

2017-01-01

Many ligand-discovery stories tell of the use of structures of protein–ligand complexes, but the contribution of structural chemistry is such a core part of finding and improving ligands that it is often overlooked. More than 800 000 crystal structures are available to the community through the Cambridge Structural Database (CSD). Individually, these structures can be of tremendous value and the collection of crystal structures is even more helpful. This article provides examples of how small-molecule crystal structures have been used to complement those of protein–ligand complexes to address challenges ranging from affinity, selectivity and bioavailability though to solubility. PMID:28291759

Why don't we find more polymorphs?

PubMed

Price, Sarah L

2013-08-01

Crystal structure prediction (CSP) studies are not limited to being a search for the most thermodynamically stable crystal structure, but play a valuable role in understanding polymorphism, as shown by interdisciplinary studies where the crystal energy landscape has been explored experimentally and computationally. CSP usually produces more thermodynamically plausible crystal structures than known polymorphs. This article illustrates some reasons why: because (i) of approximations in the calculations, particularly the neglect of thermal effects (see §1.1); (ii) of the molecular rearrangement during nucleation and growth (see §1.2); (iii) the solid-state structures observed show dynamic or static disorder, stacking faults, other defects or are not crystalline and so represent more than one calculated structure (see §1.3); (iv) the structures are metastable relative to other molecular compositions (see §1.4); (v) the right crystallization experiment has not yet been performed (see §1.5) or (vi) cannot be performed (see §1.6) and the possibility (vii) that the polymorphs are not detected or structurally characterized (see §1.7). Thus, we can only aspire to a general predictive theory for polymorphism, as this appears to require a quantitative understanding of the kinetic factors involved in all possible multi-component crystallizations. For a specific molecule, analysis of the crystal energy landscape shows the potential complexity of its crystallization behaviour.

Mechanical defenses of plant extrafloral nectaries against herbivory

PubMed Central

Gish, Moshe; Mescher, Mark C.; De Moraes, Consuelo M.

2016-01-01

ABSTRACT Extrafloral nectaries play an important role in plant defense against herbivores by providing nectar rewards that attract ants and other carnivorous insects. However, extrafloral nectaries can themselves be targets of herbivory, in addition to being exploited by nectar-robbing insects that do not provide defensive services. We recently found that the extrafloral nectaries of Vicia faba plants, as well as immediately adjacent tissues, exhibit high concentrations of chemical toxins, apparently as a defense against herbivory. Here we report that the nectary tissues of this plant also exhibit high levels of structural stiffness compared to surrounding tissues, likely due to cell wall lignification and the concentration of calcium oxalate crystals in nectary tissues, which may provide an additional deterrent to herbivore feeding on nectary tissues. PMID:27489584

From {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} to {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite chains in A{sub 6}U{sub 2}Mo{sub 4}O{sub 21} (A=Na, K, Rb, Cs) compounds: Synthesis and crystal structure of Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yagoubi, S.; Groupe de Radiochimie, Institut de Physique Nucleaire d'Orsay, Universite Paris-Sud XI, 91406 Orsay Cedex; Obbade, S., E-mail: said.obbade@phelma.grenoble-inp.f

2011-05-15

A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610 {sup o}C). -- Graphical abstract: The staking of {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite uranyl molybdate ribbons in the Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] structure. Display Omitted Highlights: {yields} Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 2} a new compound with bidimensional crystal structure, characterized by infinite uranyl molybdate chains. {yields} Crystal structure similar to these of the compounds containing Na, K, Rb. {yields} Molybdenum atoms surrounded by five oxygen atoms to form an original and strongly distorted MoO{sub 5} environment. {yields} The chains arrangement illustrates the key role of the alkaline ionic radius, in the crystal structure distortion for Cs compound.« less

Hydrogen-bond coordination in organic crystal structures: statistics, predictions and applications.

PubMed

Galek, Peter T A; Chisholm, James A; Pidcock, Elna; Wood, Peter A

2014-02-01

Statistical models to predict the number of hydrogen bonds that might be formed by any donor or acceptor atom in a crystal structure have been derived using organic structures in the Cambridge Structural Database. This hydrogen-bond coordination behaviour has been uniquely defined for more than 70 unique atom types, and has led to the development of a methodology to construct hypothetical hydrogen-bond arrangements. Comparing the constructed hydrogen-bond arrangements with known crystal structures shows promise in the assessment of structural stability, and some initial examples of industrially relevant polymorphs, co-crystals and hydrates are described.

X-ray transparent microfluidic chip for mesophase-based crystallization of membrane proteins and on-chip structure determination

DOE PAGES

Khvostichenko, Daria S.; Schieferstein, Jeremy M.; Pawate, Ashtamurthy S.; ...

2014-08-21

Crystallization from lipidic mesophase matrices is a promising route to diffraction-quality crystals and structures of membrane proteins. The microfluidic approach reported here eliminates two bottlenecks of the standard mesophase-based crystallization protocols: (i) manual preparation of viscous mesophases and (ii) manual harvesting of often small and fragile protein crystals. In the approach reported here, protein-loaded mesophases are formulated in an X-ray transparent microfluidic chip using only 60 nL of the protein solution per crystallization trial. The X-ray transparency of the chip enables diffraction data collection from multiple crystals residing in microfluidic wells, eliminating the normally required manual harvesting and mounting ofmore » individual crystals. In addition, we validated our approach by on-chip crystallization of photosynthetic reaction center, a membrane protein from Rhodobacter sphaeroides, followed by solving its structure to a resolution of 2.5 Å using X-ray diffraction data collected on-chip under ambient conditions. A moderate conformational change in hydrophilic chains of the protein was observed when comparing the on-chip, room temperature structure with known structures for which data were acquired under cryogenic conditions.« less

X-ray Transparent Microfluidic Chip for Mesophase-Based Crystallization of Membrane Proteins and On-Chip Structure Determination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khvostichenko, Daria S.; Schieferstein, Jeremy M.; Pawate, Ashtamurthy S.

2014-10-01

Crystallization from lipidic mesophase matrices is a promising route to diffraction-quality crystals and structures of membrane proteins. The microfluidic approach reported here eliminates two bottlenecks of the standard mesophase-based crystallization protocols: (i) manual preparation of viscous mesophases and (ii) manual harvesting of often small and fragile protein crystals. In the approach reported here, protein-loaded mesophases are formulated in an X-ray transparent microfluidic chip using only 60 nL of the protein solution per crystallization trial. The X-ray transparency of the chip enables diffraction data collection from multiple crystals residing in microfluidic wells, eliminating the normally required manual harvesting and mounting ofmore » individual crystals. We validated our approach by on-chip crystallization of photosynthetic reaction center, a membrane protein from Rhodobacter sphaeroides, followed by solving its structure to a resolution of 2.5 Å using X-ray diffraction data collected on-chip under ambient conditions. A moderate conformational change in hydrophilic chains of the protein was observed when comparing the on-chip, room temperature structure with known structures for which data were acquired under cryogenic conditions.« less

Toward Fully in Silico Melting Point Prediction Using Molecular Simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Y; Maginn, EJ

2013-03-01

Melting point is one of the most fundamental and practically important properties of a compound. Molecular computation of melting points. However, all of these methods simulation methods have been developed for the accurate need an experimental crystal structure as input, which means that such calculations are not really predictive since the melting point can be measured easily in experiments once a crystal structure is known. On the other hand, crystal structure prediction (CSP) has become an active field and significant progress has been made, although challenges still exist. One of the main challenges is the existence of many crystal structuresmore » (polymorphs) that are very close in energy. Thermal effects and kinetic factors make the situation even more complicated, such that it is still not trivial to predict experimental crystal structures. In this work, we exploit the fact that free energy differences are often small between crystal structures. We show that accurate melting point predictions can be made by using a reasonable crystal structure from CSP as a starting point for a free energy-based melting point calculation. The key is that most crystal structures predicted by CSP have free energies that are close to that of the experimental structure. The proposed method was tested on two rigid molecules and the results suggest that a fully in silico melting point prediction method is possible.« less

Integrative interactive visualization of crystal structure, band structure, and Brillouin zone

NASA Astrophysics Data System (ADS)

Hanson, Robert; Hinke, Ben; van Koevering, Matthew; Oses, Corey; Toher, Cormac; Hicks, David; Gossett, Eric; Plata Ramos, Jose; Curtarolo, Stefano; Aflow Collaboration

The AFLOW library is an open-access database for high throughput ab-initio calculations that serves as a resource for the dissemination of computational results in the area of materials science. Our project aims to create an interactive web-based visualization of any structure in the AFLOW database that has associate band structure data in a way that allows novel simultaneous exploration of the crystal structure, band structure, and Brillouin zone. Interactivity is obtained using two synchronized JSmol implementations, one for the crystal structure and one for the Brillouin zone, along with a D3-based band-structure diagram produced on the fly from data obtained from the AFLOW database. The current website portal (http://aflowlib.mems.duke.edu/users/jmolers/matt/website) allows interactive access and visualization of crystal structure, Brillouin zone and band structure for more than 55,000 inorganic crystal structures. This work was supported by the US Navy Office of Naval Research through a Broad Area Announcement administered by Duke University.

Sixty years from discovery to solution: crystal structure of bovine liver catalase form III

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foroughi, Leila M.; Kang, You-Na; Matzger, Adam J.

2012-03-27

The crystallization and structural characterization of bovine liver catalase (BLC) has been intensively studied for decades. Forms I and II of BLC have previously been fully characterized using single-crystal X-ray diffraction. Form III has previously been analyzed by electron microscopy, but owing to the thinness of this crystal form an X-ray crystal structure had not been determined. Here, the crystal structure of form III of BLC is presented in space group P212121, with unit-cell parameters a = 68.7, b = 173.7, c = 186.3 {angstrom}. The asymmetric unit is composed of the biological tetramer, which is packed in a tetrahedronmore » motif with three other BLC tetramers. This higher resolution structure has allowed an assessment of the previously published electron-microscopy studies.« less

Aqueous trifluorethanol solutions simulate the environment of DNA in the crystalline state.

PubMed

Kypr, J; Chládková, J; Zimulová, M; Vorlícková, M

1999-09-01

We took 28 fragments of DNA whose crystal structures were known and used CD spectroscopy to search for conditions stabilising the crystal structures in solution. All 28 fragments switched into their crystal structures in 60-80% aqueous trifluorethanol (TFE) to indicate that the crystals affected the conformation of DNA like the concentrated TFE. The fragments crystallising in the B-form also underwent cooperative TFE-induced changes that took place within the wide family of B-form structures, suggesting that the aqueous and crystal B-forms differed as well. Spermine and magnesium or calcium cations, which were contained in the crystallisation buffers, promoted or suppressed the TFE-induced changes of several fragments to indicate that the crystallisation agents can decide which of the possible structures is adopted by the DNA fragment in the crystal.

Macromolecular Crystallization in Microgravity

NASA Technical Reports Server (NTRS)

Snell, Edward H.; Helliwell, John R.

2004-01-01

The key concepts that attracted crystal growers, macromolecular or solid state, to microgravity research is that density difference fluid flows and sedimentation of the growing crystals are greatly reduced. Thus, defects and flaws in the crystals can be reduced, even eliminated, and crystal volume can be increased. Macromolecular crystallography differs from the field of crystalline semiconductors. For the latter, crystals are harnessed for their electrical behaviors. A crystal of a biological macromolecule is used instead for diffraction experiments (X-ray or neutron) to determine the three-dimensional structure of the macromolecule. The better the internal order of the crystal of a biological macromolecule then the more molecular structure detail that can be extracted. This structural information that enables an understanding of how the molecule functions. This knowledge is changing the biological and chemical sciences with major potential in understanding disease pathologies. Macromolecular structural crystallography in general is a remarkable field where physics, biology, chemistry, and mathematics meet to enable insight to the basic fundamentals of life. In this review, we examine the use of microgravity as an environment to grow macromolecular crystals. We describe the crystallization procedures used on the ground, how the resulting crystals are studied and the knowledge obtained from those crystals. We address the features desired in an ordered crystal and the techniques used to evaluate those features in detail. We then introduce the microgravity environment, the techniques to access that environment, and the theory and evidence behind the use of microgravity for crystallization experiments. We describe how ground-based laboratory techniques have been adapted to microgravity flights and look at some of the methods used to analyze the resulting data. Several case studies illustrate the physical crystal quality improvements and the macromolecular structural advances. Finally, limitations and alternatives to microgravity and future directions for this research are covered.

Feasibility of one-shot-per-crystal structure determination using Laue diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cornaby, Sterling; CHESS; Szebenyi, Doletha M. E.

Structure determination was successfully carried out using single Laue exposures from a group of lysozyme crystals. The Laue method may be a viable option for collection of one-shot-per-crystal data from microcrystals. Crystal size is an important factor in determining the number of diffraction patterns which may be obtained from a protein crystal before severe radiation damage sets in. As crystal dimensions decrease this number is reduced, eventually falling to one, at which point a complete data set must be assembled using data from multiple crystals. When only a single exposure is to be collected from each crystal, the polychromatic Lauemore » technique may be preferable to monochromatic methods owing to its simultaneous recording of a large number of fully recorded reflections per image. To assess the feasibility of solving structures using single Laue images from multiple crystals, data were collected using a ‘pink’ beam at the CHESS D1 station from groups of lysozyme crystals with dimensions of the order of 20–30 µm mounted on MicroMesh grids. Single-shot Laue data were used for structure determination by molecular replacement and correct solutions were obtained even when as few as five crystals were used.« less

Construction of crystal structure prototype database: methods and applications.

PubMed

Su, Chuanxun; Lv, Jian; Li, Quan; Wang, Hui; Zhang, Lijun; Wang, Yanchao; Ma, Yanming

2017-04-26

Crystal structure prototype data have become a useful source of information for materials discovery in the fields of crystallography, chemistry, physics, and materials science. This work reports the development of a robust and efficient method for assessing the similarity of structures on the basis of their interatomic distances. Using this method, we proposed a simple and unambiguous definition of crystal structure prototype based on hierarchical clustering theory, and constructed the crystal structure prototype database (CSPD) by filtering the known crystallographic structures in a database. With similar method, a program structure prototype analysis package (SPAP) was developed to remove similar structures in CALYPSO prediction results and extract predicted low energy structures for a separate theoretical structure database. A series of statistics describing the distribution of crystal structure prototypes in the CSPD was compiled to provide an important insight for structure prediction and high-throughput calculations. Illustrative examples of the application of the proposed database are given, including the generation of initial structures for structure prediction and determination of the prototype structure in databases. These examples demonstrate the CSPD to be a generally applicable and useful tool for materials discovery.

Construction of crystal structure prototype database: methods and applications

NASA Astrophysics Data System (ADS)

Su, Chuanxun; Lv, Jian; Li, Quan; Wang, Hui; Zhang, Lijun; Wang, Yanchao; Ma, Yanming

2017-04-01

Crystal structure prototype data have become a useful source of information for materials discovery in the fields of crystallography, chemistry, physics, and materials science. This work reports the development of a robust and efficient method for assessing the similarity of structures on the basis of their interatomic distances. Using this method, we proposed a simple and unambiguous definition of crystal structure prototype based on hierarchical clustering theory, and constructed the crystal structure prototype database (CSPD) by filtering the known crystallographic structures in a database. With similar method, a program structure prototype analysis package (SPAP) was developed to remove similar structures in CALYPSO prediction results and extract predicted low energy structures for a separate theoretical structure database. A series of statistics describing the distribution of crystal structure prototypes in the CSPD was compiled to provide an important insight for structure prediction and high-throughput calculations. Illustrative examples of the application of the proposed database are given, including the generation of initial structures for structure prediction and determination of the prototype structure in databases. These examples demonstrate the CSPD to be a generally applicable and useful tool for materials discovery.

Indium (In)- and tin (Sn)-based metal induced crystallization (MIC) on amorphous germanium (α-Ge)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Dong-Ho; Park, Jin-Hong, E-mail: jhpark9@skku.edu

Highlights: • In- and Sn-based MIC phenomenon on amorphous (α)-Ge is newly reported. • The In- and Sn-MIC phenomenon respectively started at 250 °C and 400 °C. • The Sn-MIC process presents higher sheet resistance and bigger crystal grains. - Abstract: In this paper, metal-induced crystallization (MIC) phenomenon on α-Ge by indium (In) and tin (Sn) are thoroughly investigated. In- and Sn-MIC process respectively started at 250 °C and 400 °C. Compared to the previously reported MIC samples including In-MIC, Sn-MIC process presented higher sheet resistance (similar to that of SPC) and bigger crystal grains above 50 nm (slightly smallermore » than that of SPC). According to SIMS analysis, Sn atoms diffused more slowly into Ge than In at 400 °C, providing lower density of heterogeneous nuclei induced by metals and consequently larger crystal grains.« less

Display technologies; Proceedings of the Meeting, National Chiao Tung Univ., Hsinchu, Taiwan, Dec. 17, 18, 1992

NASA Astrophysics Data System (ADS)

Chen, Shu-Hsia; Wu, Shin-Tson

1992-10-01

A broad range of interdisciplinary subjects related to display technologies is addressed, with emphasis on high-definition displays, CRTs, projection displays, materials for display application, flat-panel displays, display modeling, and polymer-dispersed liquid crystals. Particular attention is given to a CRT approach to high-definition television display, a superhigh-resolution electron gun for color display CRT, a review of active-matrix liquid-crystal displays, color design for LCD parameters in projection and direct-view applications, annealing effects on ZnS:TbF3 electroluminescent devices prepared by RF sputtering, polycrystalline silicon thin film transistors with low-temperature gate dielectrics, refractive index dispersions of liquid crystals, a new rapid-response polymer-dispersed liquid-crystal material, and improved liquid crystals for active-matrix displays using high-tilt-orientation layers. (No individual items are abstracted in this volume)

Measurement of Nonlinear Coefficients of Crystals at Terahertz Frequencies via High Field THz at the FELIX FEL

DTIC Science & Technology

2017-04-02

field terahertz, felix free electron laser, nonlinear crystal coefficients, EOARD 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT SAR 18...the Felix free electron laser. Measurements of these properties, which are crucial for designing of efficient nonlinear optical frequency...Currently, only free electron lasers are the source that can readily meet those requirements in the THz range, see Fig 2. Fig. 2 Power and tunability of the

International Workshop on Computational Condensed Matter Physics (5th) Held in Trieste, Italy on 16-18 January 1991. Programme and Abstracts

DTIC Science & Technology

1991-01-18

wave bases in the study of bulk crystals , surfces. liquids, and clusters. However, since plane waves provide uniform representation of bhysical...applied to the crystal . These statements are substantiated by converged total energy studies , and calculations of elec- tronic states, pressure...In addition, there will be one (or more) poster session(s). This activitv is co-sponsored by the Scuola Internazionale di Studi Avanzati (SISSA

Confirming the Revised C-Terminal Domain of the MscL Crystal Structure

PubMed Central

Maurer, Joshua A.; Elmore, Donald E.; Clayton, Daniel; Xiong, Li; Lester, Henry A.; Dougherty, Dennis A.

2008-01-01

The structure of the C-terminal domain of the mechanosensitive channel of large conductance (MscL) has generated significant controversy. As a result, several structures have been proposed for this region: the original crystal structure (1MSL) of the Mycobacterium tuberculosis homolog (Tb), a model of the Escherichia coli homolog, and, most recently, a revised crystal structure of Tb-MscL (2OAR). To understand which of these structures represents a physiological conformation, we measured the impact of mutations to the C-terminal domain on the thermal stability of Tb-MscL using circular dichroism and performed molecular dynamics simulations of the original and the revised crystal structures of Tb-MscL. Our results imply that this region is helical and adopts an α-helical bundle conformation similar to that observed in the E. coli MscL model and the revised Tb-MscL crystal structure. PMID:18326638

[Fine stereo structure for natural organic molecules, a preliminary study. II. Melting point influenced by structure factors].

PubMed

Lu, Y; Zheng, Q; Lu, D; Ma, P; Chen, Y

1995-06-01

Crystal structures of two compounds from Tripterygium wilfordii Hook f. have been determined by X-ray diffraction method. Structure factors influencing melting point of solid state have been analysed. Crystal class (or space group), recrystallization solvent, force between molecules and fine changes of molecular structures will all cause melting point changes of crystal substance.

On crystal versus fiber formation in dipeptide hydrogelator systems.

PubMed

Houton, Kelly A; Morris, Kyle L; Chen, Lin; Schmidtmann, Marc; Jones, James T A; Serpell, Louise C; Lloyd, Gareth O; Adams, Dave J

2012-06-26

Naphthalene dipeptides have been shown to be useful low-molecular-weight gelators. Here we have used a library to explore the relationship between the dipeptide sequence and the hydrogelation efficiency. A number of the naphthalene dipeptides are crystallizable from water, enabling us to investigate the comparison between the gel/fiber phase and the crystal phase. We succeeded in crystallizing one example directly from the gel phase. Using X-ray crystallography, molecular modeling, and X-ray fiber diffraction, we show that the molecular packing of this crystal structure differs from the structure of the gel/fiber phase. Although the crystal structures may provide important insights into stabilizing interactions, our analysis indicates a rearrangement of structural packing within the fibers. These observations are consistent with the fibrillar interactions and interatomic separations promoting 1D assembly whereas in the crystals the peptides are aligned along multiple axes, allowing 3D growth. This observation has an impact on the use of crystal structures to determine supramolecular synthons for gelators.

The Crystal Structure and Mechanism of an Unusual Oxidoreductase, GilR, Involved in Gilvocarcin V Biosynthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noinaj, Nicholas; Bosserman, Mary A.; Schickli, M. Alexandra

2012-11-26

GilR is a recently identified oxidoreductase that catalyzes the terminal step of gilvocarcin V biosynthesis and is a unique enzyme that establishes the lactone core of the polyketide-derived gilvocarcin chromophore. Gilvocarcin-type compounds form a small distinct family of anticancer agents that are involved in both photo-activated DNA-alkylation and histone H3 cross-linking. High resolution crystal structures of apoGilR and GilR in complex with its substrate pregilvocarcin V reveals that GilR belongs to the small group of a relatively new type of the vanillyl-alcohol oxidase flavoprotein family characterized by bicovalently tethered cofactors. GilR was found as a dimer, with the bicovalently attachedmore » FAD cofactor mediated through His-65 and Cys-125. Subsequent mutagenesis and functional assays indicate that Tyr-445 may be involved in reaction catalysis and in mediating the covalent attachment of FAD, whereas Tyr-448 serves as an essential residue initiating the catalysis by swinging away from the active site to accommodate binding of the 6R-configured substrate and consequently abstracting the proton of the hydroxyl residue of the substrate hemiacetal 6-OH group. These studies lay the groundwork for future enzyme engineering to broaden the substrate specificity of this bottleneck enzyme of the gilvocarcin biosynthetic pathway for the development of novel anti-cancer therapeutics.« less

Remarkably improved field emission of TiO{sub 2} nanotube arrays by annealing atmosphere engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Ai-Zhen; Wang, Cheng-Wei, E-mail: cwwang@nwnu.edu.cn; Chen, Jian-Biao

2015-10-15

Highlights: • TNAs were prepared by anodization and annealed in different atmospheres. • The crystal structure and electronic properties of the prepared TNAs were investigated. • The field emission of TNAs was highly dependent on annealing atmosphere. • A low turn-on of 2.44 V/μm was obtained for TNAs annealed in H{sub 2} atmosphere. - Abstract: Highly ordered TiO{sub 2} nanotube arrays (TNAs) were prepared by anodization, and followed by annealing in the atmospheres of Air, Vacuum, Ar, and H{sub 2}. The effect of annealing atmosphere on the crystal structure, composition, and electronic properties of TNAs were systematically investigated. Raman andmore » EDS results indicated that the TNAs annealed in anaerobic atmospheres contained more oxygen vacancies, which result in the substantially improved electron transport properties and reduced work function. Moreover, it was found that the FE properties of TNAs were highly dependent on the annealing atmosphere. By engineering the annealing atmosphere, the turn-on field as low as 2.44 V/μm can be obtained from TNAs annealed in H{sub 2}, which was much lower than the value of 18.23 V/μm from the TNAs annealed in the commonly used atmosphere of Air. Our work suggests an instructive and attractive way to fabricate high performance TNAs field emitters.« less

Complexes of cis-dioxomolybdenum(VI) and oxovanadium(IV) with a tridentate ONS donor ligand: Synthesis, spectroscopic properties, X-ray crystal structure and catalytic activity

NASA Astrophysics Data System (ADS)

Fayed, Ahmed M.; Elsayed, Shadia A.; El-Hendawy, Ahmed M.; Mostafa, Mohamed R.

2014-08-01

New cis-dioxomolybdenum(VI) and oxovanadium(IV) complexes of the Schiff base, derived from S-methyl dithiocarbazate and 2,3-dihydroxybenzaldehyde (H2dhsm), have been synthesized. The complexes of the type cis-[MoO2(dhsm)] (1a), cis-[MoO2(dhsm)(D)] (1b-1d) [D = neutral monodentate ligand; EtOH, pyridine (py) or imidazole (imz)], [VO(dhsm)(Nsbnd N)] (2a, 2b) [Nsbnd N = 2,2‧-bipyridine (bipy) or 1,10-phenanthroline (phen)] and [VO(dhsm)] (2c) have been isolated, characterized by 1H NMR, IR, UV-Vis and EPR spectral studies and investigated by cyclic voltammetry. The X-ray crystal structure of cis-[MoO2(dhsm)(EtOH)] (1b) has been determined and shows that the complex has a distorted octahedral geometry in which the H2dhsm behaves as a dianionic ONS tridentate ligand coordinating via phenoxide oxygen, hydrazinic nitrogen and thiolate sulfur. The oxomolybdenum(IV) complex [MoO(dhsm)] (1e) has obtained from dioxomolybdenum(VI) complex (1b) by oxo abstraction with PPh3. The reactivity of the complexes toward catalytic oxidation of alcohols in the presence of H2O2 and t-BuOOH as co-oxidants under solvent free conditions is reported.

The crystal structure and mechanism of an unusual oxidoreductase, GilR, involved in gilvocarcin V biosynthesis.

PubMed

Noinaj, Nicholas; Bosserman, Mary A; Schickli, M Alexandra; Piszczek, Grzegorz; Kharel, Madan K; Pahari, Pallab; Buchanan, Susan K; Rohr, Jürgen

2011-07-01

GilR is a recently identified oxidoreductase that catalyzes the terminal step of gilvocarcin V biosynthesis and is a unique enzyme that establishes the lactone core of the polyketide-derived gilvocarcin chromophore. Gilvocarcin-type compounds form a small distinct family of anticancer agents that are involved in both photo-activated DNA-alkylation and histone H3 cross-linking. High resolution crystal structures of apoGilR and GilR in complex with its substrate pregilvocarcin V reveals that GilR belongs to the small group of a relatively new type of the vanillyl-alcohol oxidase flavoprotein family characterized by bicovalently tethered cofactors. GilR was found as a dimer, with the bicovalently attached FAD cofactor mediated through His-65 and Cys-125. Subsequent mutagenesis and functional assays indicate that Tyr-445 may be involved in reaction catalysis and in mediating the covalent attachment of FAD, whereas Tyr-448 serves as an essential residue initiating the catalysis by swinging away from the active site to accommodate binding of the 6R-configured substrate and consequently abstracting the proton of the hydroxyl residue of the substrate hemiacetal 6-OH group. These studies lay the groundwork for future enzyme engineering to broaden the substrate specificity of this bottleneck enzyme of the gilvocarcin biosynthetic pathway for the development of novel anti-cancer therapeutics.

Synthesis of boron suboxide from boron and boric acid under mild pressure and temperature conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiao, Xiaopeng; Jin, Hua; Ding, Zhanhui

2011-05-15

Graphical abstract: Well-crystallized and icosahedral B{sub 6}O crystals were prepared by reacting boron and boric acid at milder reaction conditions (1 GPa and 1300 {sup o}C for 2 h) as compared to previous work.. Research highlights: {yields} Well-crystallized icosahedral B{sub 6}O was synthesized by reacting boric acid and boron. {yields} The synthesis conditions (1 GPa and 1300 {sup o}C for 2 h) are milder in comparison with previous work. {yields} The more practical synthesis method may make B{sub 6}O as a potential substitute for diamond in industry. -- Abstract: Boron suboxide (B{sub 6}O) was synthesized by reacting boron and boricmore » acid (H{sub 3}BO{sub 3}) at pressures between 1 and 10 GPa, and at temperatures between 1300 and 1400 {sup o}C. The B{sub 6}O samples prepared were icosahedral with diameters ranging from 20 to 300 nm. Well-crystallized and icosahedral crystals with an average size of {approx}100 nm can be obtained at milder reaction conditions (1 GPa and 1300 {sup o}C for 2 h) as compared to previous work. The bulk B{sub 6}O sample was stable in air at 600 {sup o}C and then slowly oxidized up to 1000 {sup o}C. The relatively mild synthetic conditions developed in this study provide a more practical synthesis of B{sub 6}O, which may potentially be used as a substitute for diamond in industry as a new superhard material.« less

Luminescence and radiation resistance of undoped NaI crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shiran, N., E-mail: shiran@isc.kharkov.com; Boiaryntseva, I.; Gektin, A.

2014-11-15

Highlights: • The performance of NaI scintillators depends on luminescence properties. • A criterion of crystals’ purity level is radiation colorability at room temperature. • The traces of the most dangerous impurities were detected. • Crucial role in efficiency of pure NaI scintillator play the crystal perfection. - Abstract: Undoped NaI single crystal is an excellent scintillator at low temperature. However, scintillation parameters of different quality crystals vary in a wide range, significantly exceeding measurement error. Experimental data demonstrate the features of luminescence, radiation induced coloration, and afterglow dependence on the quality of nominally pure crystals. It is found thatmore » defects level that allows to elucidate artefacts introduced by traces of harmful impurities corresponds to 3 × 10{sup 15} cm{sup −3} that significantly overhead accuracy of chemical and absorption analysis. It is shown that special raw material treatment before and during the single crystal growth allows to reach NaI purity level that avoids impurities influence to the basic luminescence data.« less

A STUDY OF DISLOCATION STRUCTURE OF SUBBOUNDARIES IN MOLYBDENUM SINGLE CRYSTALS,

DTIC Science & Technology

MOLYBDENUM, *DISLOCATIONS), GRAIN STRUCTURES(METALLURGY), SINGLE CRYSTALS, ZONE MELTING, ELECTRON BEAM MELTING, GRAIN BOUNDARIES, MATHEMATICAL ANALYSIS, ETCHED CRYSTALS, ETCHING, ELECTROEROSIVE MACHINING, CHINA

Growth and characterization of new semiorganic nonlinear optical and piezoelectric lithium sulfate monohydrate oxalate single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yadav, Harsh; Sinha, Nidhi; Kumar, Binay, E-mail: b3kumar69@yahoo.co.in

2015-04-15

Highlights: • A new semiorganic single crystal of LSO grown by slow evaporation technique. • Morphological studies of the LSO crystal deduced by BFDH law. • In the UV–vis spectrum wide transparent region and large band gap were found. • SHG is equal to KDP crystal and d{sub 33} was found to be equal to 6pC/N. • Grown crystal belongs to softer category. - Abstract: New semiorganic crystal of lithium sulfate monohydrate oxalate (LSO) for nonlinear application was synthesized by controlled slow evaporation method. The growth rate of various planes of the grown crystal was estimated by morphological study. Singlemore » crystal XRD analysis confirmed that the crystal belongs to triclinic lattice with space group P1. High transparency (∼95%) with large band gap (4.57 eV) was analyzed by UV–vis studies. FTIR and Raman spectroscopy were used to identify various functional groups present in the LSO crystal. SHG efficiency was found to be equal to the KDP crystal. Thermal stability (up to 117.54 °C) and melting point (242 °C) of the crystal were studied by TG-DTA. In dielectric measurements, the value of dielectric constant decreases with increase in frequency. Hardness studies confirmed soft nature of crystals. The piezoelectric coefficient was found to be 6pC/N along [0 0 1].« less

Self-powdering and nonlinear optical domain structures in ferroelastic β‧-Gd2(MoO4)3 crystals formed in glass

NASA Astrophysics Data System (ADS)

Tsukada, Y.; Honma, T.; Komatsu, T.

2009-08-01

Ferroelastic β'-Gd 2(MoO 4) 3, (GMO), crystals are formed through the crystallization of 21.25Gd 2O 3-63.75MoO 3-15B 2O 3 glass (mol%), and two scientific curious phenomena are observed. (1) GMO crystals formed in the crystallization break into small pieces with a triangular prism or pyramid shape having a length of 50-500 μm spontaneously during the crystallizations in the inside of an electric furnace, not during the cooling in air after the crystallization. This phenomenon is called "self-powdering phenomenon during crystallization" in this paper. (2) Each self-powdered GMO crystal grain shows a periodic domain structure with different refractive indices, and a spatially periodic second harmonic generation (SHG) depending on the domain structure is observed. It is proposed from polarized micro-Raman scattering spectra and the azimuthal dependence of second harmonic intensities that GMO crystals are oriented in each crystal grain and the orientation of (MoO 4) 2- tetrahedra in GMO crystals changes periodically due to spontaneous strains in ferroelastic GMO crystals.

Correlation between hierarchical structure of crystal networks and macroscopic performance of mesoscopic soft materials and engineering principles.

PubMed

Lin, Naibo; Liu, Xiang Yang

2015-11-07

This review examines how the concepts and ideas of crystallization can be extended further and applied to the field of mesoscopic soft materials. It concerns the structural characteristics vs. the macroscopic performance, and the formation mechanism of crystal networks. Although this subject can be discussed in a broad sense across the area of mesoscopic soft materials, our main focus is on supramolecular materials, spider and silkworm silks, and biominerals. First, the occurrence of a hierarchical structure, i.e. crystal network and domain network structures, will facilitate the formation kinetics of mesoscopic phases and boost up the macroscopic performance of materials in some cases (i.e. spider silk fibres). Second, the structure and performance of materials can be correlated in some way by the four factors: topology, correlation length, symmetry/ordering, and strength of association of crystal networks. Moreover, four different kinetic paths of crystal network formation are identified, namely, one-step process of assembly, two-step process of assembly, mixed mode of assembly and foreign molecule mediated assembly. Based on the basic mechanisms of crystal nucleation and growth, the formation of crystal networks, such as crystallographic mismatch (or noncrystallographic) branching (tip branching and fibre side branching) and fibre/polymeric side merging, are reviewed. This facilitates the rational design and construction of crystal networks in supramolecular materials. In this context, the (re-)construction of a hierarchical crystal network structure can be implemented by thermal, precipitate, chemical, and sonication stimuli. As another important class of soft materials, the unusual mechanical performance of spider and silkworm silk fibres are reviewed in comparison with the regenerated silk protein derivatives. It follows that the considerably larger breaking stress and unusual breaking strain of spider silk fibres vs. silkworm silk fibres can be interpreted according to the synergistically correlated hierarchical structures of the domain and crystal networks, which can be quantified by the hierarchical structural correlation and the four structural parameters. Based on the concept of crystal networks, the new understanding acquired will transfer the research and engineering of mesoscopic materials, particularly, soft functional materials, to a new phase.

Computed crystal energy landscapes for understanding and predicting organic crystal structures and polymorphism.

PubMed

Price, Sarah Sally L

2009-01-20

The phenomenon of polymorphism, the ability of a molecule to adopt more than one crystal structure, is a well-established property of crystalline solids. The possible variations in physical properties between polymorphs make the reliable reproduction of a crystalline form essential for all research using organic materials, as well as quality control in manufacture. Thus, the last two decades have seen both an increase in interest in polymorphism and the availability of the computer power needed to make the computational prediction of organic crystal structures a practical possibility. In the past decade, researchers have made considerable improvements in the theoretical basis for calculating the sets of structures that are within the energy range of possible polymorphism, called crystal energy landscapes. It is common to find that a molecule has a wide variety of ways of packing with lattice energy within a few kilojoules per mole of the most stable structure. However, as we develop methods to search for and characterize "all" solid forms, it is also now usual for polymorphs and solvates to be found. Thus, the computed crystal energy landscape reflects and to an increasing extent "predicts" the emerging complexity of the solid state observed for many organic molecules. This Account will discuss the ways in which the calculation of the crystal energy landscape of a molecule can be used as a complementary technique to solid form screening for polymorphs. Current methods can predict the known crystal structure, even under "blind test" conditions, but such successes are generally restricted to those structures that are the most stable over a wide range of thermodynamic conditions. The other low-energy structures can be alternative polymorphs, which have sometimes been found in later experimental studies. Examining the computed structures reveals the various compromises between close packing, hydrogen bonding, and pi-pi stacking that can result in energetically feasible structures. Indeed, we have observed that systems with many almost equi-energetic structures that contain a common interchangeable motif correlate with a tendency to disorder and problems with control of the crystallization product. Thus, contrasting the computed crystal energy landscape with the known crystal structures of a given molecule provides a valuable complement to solid form screening, and the examination of the low-energy structures often leads to a rationalization of the forms found.

Structural, microstructural and vibrational analyses of the monoclinic tungstate BiLuWO{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ait Ahsaine, H.; Taoufyq, A.; Institut Matériaux Microélectronique et Nanosciences de Provence, IM2NP, UMR CNRS 7334, Université de Toulon, BP 20132, 83957 La Garde Cedex

2014-10-15

The bismuth lutetium tungstate phase BiLuWO{sub 6} has been prepared using a solid state route with stoichiometric mixtures of oxide precursors. The obtained polycrystalline phase has been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. In the first step, the crystal structure has been refined using Rietveld method: the crystal cell was resolved using monoclinic system (parameters a, b, c, β) with space group A2/m. SEM images showed the presence of large crystallites with a constant local nominal composition (BiLuW). TEM analyses showed that the actual local structure could be better representedmore » by a superlattice (a, 2b, c, β) associated with space groups P2 or P2/m. The Raman spectroscopy showed the presence of vibrational bands similar to those observed in the compounds BiREWO{sub 6} with RE=Y, Gd, Nd. However, these vibrational bands were characterized by large full width at half maximum, probably resulting from the long range Bi/Lu disorder and local WO{sub 6} octahedron distortions in the structure. - Graphical abstract: The average structure of BiLuWO{sub 6} determined from X-ray diffraction data can be represented by A2/m space group. Experimental Electron Diffraction patterns along the [0vw] zone axes of the monoclinic structure and associated simulated patterns show the existence of a monoclinic superstructure with space group P2 or P2/m. - Highlights: • A new monoclinic BiLuWO{sub 6} phase has been elaborated from solid-state reaction. • The space group of the monoclinic disordered average structure should be A2/m. • Transmission electron microscopy leads to a superlattice with P2/m space group. • Raman spectroscopy suggests existence of local disorder.« less

Crystallographic Topology 2: Overview and Work in Progress

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, C.K.

1999-08-01

This overview describes an application of contemporary geometric topology and stochastic process concepts to structural crystallography. In this application, crystallographic groups become orbifolds, crystal structures become Morse functions on orbifolds, and vibrating atoms in a crystal become vector valued Gaussian measures with the Radon-Nikodym property. Intended crystallographic benefits include new methods for visualization of space groups and crystal structures, analysis of the thermal motion patterns seen in ORTEP drawings, and a classification scheme for crystal structures based on their Heegaard splitting properties.

[Crystal structure of SMU.2055 protein from Streptococcus mutans and its small molecule inhibitors design and selection].

PubMed

Xiaodan, Chen; Xiurong, Zhan; Xinyu, Wu; Chunyan, Zhao; Wanghong, Zhao

2015-04-01

The aim of this study is to analyze the three-dimensional crystal structure of SMU.2055 protein, a putative acetyltransferase from the major caries pathogen Streptococcus mutans (S. mutans). The design and selection of the structure-based small molecule inhibitors are also studied. The three-dimensional crystal structure of SMU.2055 protein was obtained by structural genomics research methods of gene cloning and expression, protein purification with Ni²⁺-chelating affinity chromatography, crystal screening, and X-ray diffraction data collection. An inhibitor virtual model matching with its target protein structure was set up using computer-aided drug design methods, virtual screening and fine docking, and Libdock and Autodock procedures. The crystal of SMU.2055 protein was obtained, and its three-dimensional crystal structure was analyzed. This crystal was diffracted to a resolution of 0.23 nm. It belongs to orthorhombic space group C222(1), with unit cell parameters of a = 9.20 nm, b = 9.46 nm, and c = 19.39 nm. The asymmetric unit contained four molecules, with a solvent content of 56.7%. Moreover, five small molecule compounds, whose structure matched with that of the target protein in high degree, were designed and selected. Protein crystallography research of S. mutans SMU.2055 helps to understand the structures and functions of proteins from S. mutans at the atomic level. These five compounds may be considered as effective inhibitors to SMU.2055. The virtual model of small molecule inhibitors we built will lay a foundation to the anticaries research based on the crystal structure of proteins.

Phase transformation of Ca{sub 4}[Al{sub 6}O{sub 12}]SO{sub 4} and its disordered crystal structure at 1073 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurokawa, Daisuke; R and D Center, Taiheiyo Cement Corporation, Chiba 285-8655; Takeda, Seiya

The phase transformation of Ca{sub 4}[Al{sub 6}O{sub 12}]SO{sub 4} and the crystal structure of its high-temperature phase were investigated by differential thermal analysis, temperature-dependent Raman spectroscopy and high-temperature X-ray powder diffraction (CuKα{sub 1}). We determined the starting temperature of the orthorhombic-to-cubic transformation during heating (=711 K) and that of the reverse transformation during cooling (=742 K). The thermal hysteresis was negative (=−31 K), suggesting the thermoelasticity of the transformation. The space group of the high temperature phase is I4{sup ¯}3m with the unit-cell dimensions of a=0.92426(2) nm and V=0.78955(2) nm{sup 3} (Z=2) at 1073 K. The initial structural model wasmore » derived by the direct methods and further refined by the Rietveld method. The final structural model showed the orientational disordering of SO{sub 4} tetrahedra. The maximum-entropy method-based pattern fitting method was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. At around the transformation temperature during heating, the vibrational spectra, corresponding to the Raman-active SO{sub 4} internal stretching mode, showed the continuous and gradual change in the slope of full width at half maximum versus temperature curve. This strongly suggests that the orthorhombic-to-cubic phase transformation would be principally accompanied by the statistical disordering in orientation of the SO{sub 4} tetrahedra, without distinct dynamical reorientation. - Graphical abstract: (Left) Three-dimensional electron-density distributions of the SO{sub 4} tetrahedron with the split-atom model, and (right) a bird's eye view of electron densities on the plane parallel to (111). - Highlights: • Crystal structure of Ca{sub 4}[Al{sub 6}O{sub 12}]SO{sub 4} at 1073 K is determined by powder XRD. • The atom arrangements are represented by the split-atom model. • The MPF method is used to confirm the validity of the model. • The phase transition is accompanied by orientational disordering of SO{sub 4} tetrahedra.« less

Crystal structure and ion conductivity of a new mixed-anion phosphate LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Sung-Chul; Lee, Mi-Sun; Kang, Jinyeong

2015-05-15

A new lithium-containing phosphate, LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7}, was prepared by a solid-state reaction, and it was characterized by an ab initio structure determination method on the basis of synchrotron powder X-ray diffraction data. LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} was found to be orthorhombic (space group Pnma) with lattice parameters a=9.0387(1) Å, b=10.6072(1) Å, c=8.3065(1) Å, and V=796.39(1) Å{sup 3}. The structure features infinite [Mg{sub 3}O{sub 10}]{sub ∞} layers that are parallel to the bc plane and that are interconnected along the a axis by PO{sub 4} and P{sub 2}O{sub 7} groups. The [Mg{sub 3}O{sub 10}]{sub ∞} layer containsmore » Mg{sub 3}O{sub 14} trimers that are formed by three edge-shared MgO{sub 6} octahedra. The PO{sub 4} and P{sub 2}O{sub 7} groups are located alternatively between [Mg{sub 3}O{sub 10}]{sub ∞} layers. This gives rise to a three-dimensional framework that contains large tunnels along the directions [1 0 0] and [0 1 0]; the Li{sup +} ions are stabilized in these tunnels. AC impedance spectroscopy shows that LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} has an ionic conductivity of 3.40×10{sup −5} S cm{sup −1} at 769 K, with an activation energy of 1.17 eV. - Graphical abstract: Polyhedral view of LiMg3(PO4)P2O7. Li+ ions are represented by orange spheres, MgO6 groups by octahedra, and PO4 groups by tetrahedra. - Highlights: • New compound LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} is reported. • The crystal structure is investigated by synchrotron XRD analysis. • The structure features [Mg{sub 3}O{sub 10}]{sub ∞} layers with interconnecting PO{sub 4} and P{sub 2}O{sub 7} groups. • Correlation between the crystal structure and ionic conductivity is discussed.« less

Precision mechanical structure of an ultra-high-resolution spectrometer for inelastic X-ray scattering instrument

DOEpatents

Shu, Deming; Shvydko, Yuri; Stoupin, Stanislav A.; Khachatryan, Ruben; Goetze, Kurt A.; Roberts, Timothy

2015-04-14

A method and an ultrahigh-resolution spectrometer including a precision mechanical structure for positioning inelastic X-ray scattering optics are provided. The spectrometer includes an X-ray monochromator and an X-ray analyzer, each including X-ray optics of a collimating (C) crystal, a pair of dispersing (D) element crystals, anomalous transmission filter (F) and a wavelength (W) selector crystal. A respective precision mechanical structure is provided with the X-ray monochromator and the X-ray analyzer. The precision mechanical structure includes a base plate, such as an aluminum base plate; positioning stages for D-crystal alignment; positioning stages with an incline sensor for C/F/W-crystal alignment, and the positioning stages including flexure-based high-stiffness structure.

Synthesis and structural study of 4-(2-chlorophenyl)-2-ethoxy-5,6,7,8,9,10-hexahydrocycloocta[B]pyridine-3-carbonitrile

NASA Astrophysics Data System (ADS)

Fathima, K. Saiadali; Vasumathi, M.; Anitha, K.

2016-05-01

The novel organic material C20H21ClN2O was synthesized by One-Pot synthesis method and the single crystals were grown by slow evaporation solution growth technique. The crystal structure was elucidated by subjecting the grown crystals to the single crystal x-ray diffraction analysis and was refined by full matrix least-squares method to R=0.039 for 2746 reflections. Crystal system of the grown crystal was found to be monoclinic with the space group P21/a and a=9.196(4) Å, b=13.449(4) Å, c=14.818(4) Å, β= 101.542(3)°, V=1795.6(11) Å3 and Z=4. In this crystal structure, cyclooctanone prefers to reside in a chair-boat conformation. The structure is stabilized by attractive molecular force such as CH/π interaction called hydrophobic interaction.

Structural properties and defects of GaN crystals grown at ultra-high pressures: A molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Gao, Tinghong; Li, Yidan; Xie, Quan; Tian, Zean; Chen, Qian; Liang, Yongchao; Ren, Lei; Hu, Xuechen

2018-01-01

The growth of GaN crystals at different pressures was studied by molecular dynamics simulation employing the Stillinger-Weber potential, and their structural properties and defects were characterized using the radial distribution function, the Voronoi polyhedron index method, and a suitable visualization technology. Crystal structures formed at 0, 1, 5, 10, and 20 GPa featured an overwhelming number of <4 0 0 0> Voronoi polyhedra, whereas amorphous structures comprising numerous disordered polyhedra were produced at 50 GPa. During quenching, coherent twin boundaries were easily formed between zinc-blende and wurtzite crystal structures in GaN. Notably, point defects usually appeared at low pressure, whereas dislocations were observed at high pressure, since the simultaneous growth of two crystal grains with different crystal orientations and their boundary expansion was hindered in the latter case, resulting in the formation of a dislocation between these grains.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Zhe, E-mail: zhenzhe1201@sina.com; Yang, Lei; Hang, Yin

Highly transparent Dy{sup 3+}-doped terbium gallium garnet (TGG) single crystal was grown by Czochralski (Cz) method. Phase composition of the crystal was tested by XRD measurements. The distribution coefficient of Dy{sup 3+} in the crystal was obtained. The optical and magneto-optical properties were analyzed in detail, and magnetic properties of the Dy{sup 3+}-TGG crystal were studied. The paramagnetic behavior is observed down to 10 K. The as-grown crystal exhibited high optical transmittance, particularly in the visible region. The Faraday rotation was investigated over visible and near-infrared regions (VIS–NIR) at room temperature. The Verdet constants increase at measured wavelengths and highmore » thermal stability was found in Dy{sup 3+}-doped TGG, as compared to the properties of pure TGG, indicating that Dy{sup 3+}-doped crystals are preferable for magneto-active materials used in Faraday devices at VIS–NIR wavelengths. - Graphical abstract: Highly transparent Dy{sup 3+}-doped terbium gallium garnet (TGG) and pure TGG single crystals were grown by Czochralski method. The Dy{sup 3+}-doped TGG possesses 20–30% higher Verdet values in reference to TGG independently on wavelength.« less

Discovering H-bonding rules in crystals with inductive logic programming.

PubMed

Ando, Howard Y; Dehaspe, Luc; Luyten, Walter; Van Craenenbroeck, Elke; Vandecasteele, Henk; Van Meervelt, Luc

2006-01-01

In the domain of crystal engineering, various schemes have been proposed for the classification of hydrogen bonding (H-bonding) patterns observed in 3D crystal structures. In this study, the aim is to complement these schemes with rules that predict H-bonding in crystals from 2D structural information only. Modern computational power and the advances in inductive logic programming (ILP) can now provide computational chemistry with the opportunity for extracting structure-specific rules from large databases that can be incorporated into expert systems. ILP technology is here applied to H-bonding in crystals to develop a self-extracting expert system utilizing data in the Cambridge Structural Database of small molecule crystal structures. A clear increase in performance was observed when the ILP system DMax was allowed to refer to the local structural environment of the possible H-bond donor/acceptor pairs. This ability distinguishes ILP from more traditional approaches that build rules on the basis of global molecular properties.

Study on sensing property of one-dimensional ring mirror-defect photonic crystal

NASA Astrophysics Data System (ADS)

Chen, Ying; Luo, Pei; Cao, Huiying; Zhao, Zhiyong; Zhu, Qiguang

2018-02-01

Based on the photon localization and the photonic bandgap characteristics of photonic crystals (PCs), one-dimensional (1D) ring mirror-defect photonic crystal structure is proposed. Due to the introduction of mirror structure, a defect cavity is formed in the center of the photonic crystal, and then the resonant transmission peak can be obtained in the bandgap of transmission spectrum. The transfer matrix method is used to establish the relationship model between the resonant transmission peak and the structure parameters of the photonic crystals. Using the rectangular air gate photonic crystal structure, the dynamic monitoring of the detected gas sample parameters can be achieved from the shift of the resonant transmission peak. The simulation results show that the Q-value can attain to 1739.48 and the sensitivity can attain to 1642 nm ṡ RIU-1, which demonstrates the effectiveness of the sensing structure. The structure can provide certain theoretical reference for air pollution monitoring and gas component analysis.

Development and photoelectric properties of In/p-Ag{sub 3}AsS{sub 3} surface-barrier structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rud', V. Yu., E-mail: rudvas@spbstu.ru; Rud', Yu. V.; Terukov, E. I.

2010-08-15

Homogeneous p-Ag{sub 3}AsS{sub 3} bulk single crystals with rhombic structure have been grown by planar crystallization from melts with atomic composition corresponding to this ternary compound. Photosensitive surface-barrier structures based on the interface between the surface of these crystals and thin films of pure indium are fabricated for the first time. The photosensitivity of fabricated structures is studied in natural and linearly polarized light. Photosensitivity spectra of In/p-Ag{sub 3}AsS{sub 3} structures are measured for the first time and used to determine the nature and energy of interband transitions in p-Ag{sub 3}AsS{sub 3} crystals. The phenomenon of natural photopleochroism is studiedmore » for surface-barrier structures grown on oriented p-Ag{sub 3}AsS{sub 3} single crystals. It is concluded that Ag{sub 3}AsS{sub 3} single crystals can be used in photoconverters of natural and linearly polarized light.« less

Generation of crystal structures using known crystal structures as analogues

PubMed Central

Cole, Jason C.; Groom, Colin R.; Read, Murray G.; Giangreco, Ilenia; McCabe, Patrick; Reilly, Anthony M.; Shields, Gregory P.

2016-01-01

This analysis attempts to answer the question of whether similar molecules crystallize in a similar manner. An analysis of structures in the Cambridge Structural Database shows that the answer is yes – sometimes they do, particularly for single-component structures. However, one does need to define what we mean by similar in both cases. Building on this observation we then demonstrate how this correlation between shape similarity and packing similarity can be used to generate potential lattices for molecules with no known crystal structure. Simple intermolecular interaction potentials can be used to minimize these potential lattices. Finally we discuss the many limitations of this approach. PMID:27484374

Large structural modulations in the relaxor ferroelectric and intermediate state of strontium rich members (x>0.6) of the Sr{sub x}Ba{sub 1−x}Nb{sub 2}O{sub 6} (sbn) solid solution series

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graetsch, H.A., E-mail: heribert.graetsch@rub.de

The amplitudes of the positional, occupational and adp modulations of sbn mixed crystals are strongly enhanced for high strontium contents. The increase of structural modulations is accompanied by reduced spontaneous electric polarization largely due to smaller off-center shifts of the niobium atoms. Beyond the room temperature ferroelectric – intermediate transition near x=0.77, anomal large U{sub 33} atomic displacement parameters of the niobium atoms indicate static disorder caused by loss of orientational coupling between residual shifts of Nb atoms in neighboring NbO{sub 6} octahedra. Change of satellite intensities show a reduction from two-dimensional to one-dimensional modulation which is not consistent withmore » tetragonal symmetry. The pseudo-tetragonally twinned crystal structure of sbn82 was refined in the orthorhombic super-space group A2mm(½0γ)000. The apparent tetragonal symmetry of the other investigated sbn samples also seems to be due to pseudo tetragonal twinning with equal twin volumes. The modulations mainly consist of cooperatively tilted NbO{sub 6} octahedra and wave-like ordered incomplete occupation of the largest cation sites (Me2a and b) by Ba{sup 2+} and Sr{sup 2+}. Furthermore, the atomic displacement parameters of the Me2 sites are strongly modulated. - Graphical abstract: Satellite reflections and modulation coefficients in the solid solution series Sr{sub x}Ba{sub 1−x}Nb{sub 2}O{sub 6}. - Highlights: • The modulationed structures are refined for the whole composition range of sbn32–sbn82 in tetragonal and orthorhombic setting. • The amplitudes of positional, occupational and adp modulations increase strongly with the strontium content. • Evidence is presented that the sbn crystals are pseudo tetragonally twinned. • The ferroelectric–intermediate paraelectric transition is not accompanied by a change of symmetry. • Anomal adp of intermediate (non-ferroelectric) sbn82 indicate loss of coupling between off-center shifts of neighboring niobium.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Hua-Jun, E-mail: cszzl772002@yeah.net; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002

Two quaternary sulfides RE{sub 3}Sb{sub 0.33}SiS{sub 7} (RE=La, Pr) have been prepared from stoichiometric mixtures of elements at 1223 K in an evacuated silica tube. They are the first examples of chalcogenides in the quaternary RE/Si/Sb/Q (RE=rare earth metal; Q=S, Se, Te) system. These two isostructural materials crystallize in the Ce{sub 3}Al{sub 1.67}S{sub 7} structure type in the hexagonal space group P6{sub 3}. Their structure features one-dimensional chains of face-sharing SbS{sub 6} octahedra running parallel to the c direction surrounded by the discrete SiS{sub 4} tetrahedra and RE cations. The La{sub 3}Sb{sub 0.33}SiS{sub 7} exhibits a SHG signal about 0.5more » times that of the commercially used IR NLO material AgGaS{sub 2} at 2.05 μm laser. The optical gap of 1.92 eV for La{sub 3}Sb{sub 0.33}SiS{sub 7} was deduced from UV/Vis reflectance spectroscopy. - Graphical abstract: The RE{sub 3}Sb{sub 0.33}SiS{sub 7} (RE=La, Pr), crystalling in the Ce{sub 3}Al{sub 1.67}S{sub 7} structure type, have been prepared. The La{sub 3}Sb{sub 0.33}SiS{sub 7} exhibits a SHG signal about 0.5 times that of the IR NLO material AgGaS{sub 2}. - Highlights: • The RE{sub 3}Sb{sub 0.33}SiS{sub 7} (RE=La, Pr), crystalling in the Ce{sub 3}Al{sub 1.67}S{sub 7} structure type, have been prepared. • The La{sub 3}Sb{sub 0.33}SiS{sub 7} exhibits a SHG signal about 0.5 times that of the IR NLO material AgGaS{sub 2}. • The optical gap of 1.92 eV for La{sub 3}Sb{sub 0.33}SiS{sub 7} was deduced from UV/Vis reflectance spectroscopy.« less

Experimental and theoretical investigations of the polar intermetallics SrPt{sub 3}Al{sub 2} and Sr{sub 2}Pd{sub 2}Al

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stegemann, Frank; Benndorf, Christopher; Touzani, Rachid St.

SrPt{sub 3}Al{sub 2}, a CaCu{sub 5} relative (P6/mmm; a = 566.29(3), c = 389.39(3) pm; wR{sub 2} = 0.0202, 121 F{sup 2} values, 9 parameters), and Sr{sub 2}Pd{sub 2}Al, isostructural to Ca{sub 2}Pt{sub 2}Ge (Fdd2; a = 1041.45(5), b = 1558.24(7), c = 604.37(3) pm; wR{sub 2} = 0.0291, 844 F{sup 2} values, 25 parameters) have been prepared from the elements. The crystal structures have been investigated by single crystal X-ray diffraction. Structural relaxation confirmed the electronic stability of SrPt{sub 3}Al{sub 2}, while orthorhombic Sr{sub 2}Pd{sub 2}Al might be a metastable polymorph as it is energetically competitive to its monoclinicmore » variant. Both compounds are predicted to be metallic conductors as their density-of-states (DOS) are non-zero at the Fermi level. COHP bonding analysis coupled with Bader effective charge analysis suggest that the title compounds are polar intermetallic phases in which strong Pt–Al and Pd–Al covalent bonds are present, while a significant electron transfer from Sr atoms to the [Pt{sub 3}Al{sub 2}]{sup δ–} or [Pd{sub 2}Al]{sup δ–} network is found. - Graphical abstract: Chains of Pd atoms in the crystal structure of Sr{sub 2}Pd{sub 2}Al get connected by Al atoms in the shape of a distorted tetrahedra. The band structure calculations confirm weak Pd–Pd interactions. - Highlights: • SrPt{sub 3}Al{sub 2} and Sr{sub 2}Pd{sub 2}Al discovered and crystallographically investigated. • DFT predicts the here reported orthorhombic Sr{sub 2}Pd{sub 2}Al to be competitive in energy to the presently unknown monoclinic Sr{sub 2}Pd{sub 2}Al. • Bader charge analysis indicates SrPt{sub 3}Al{sub 2} and Sr{sub 2}Pd{sub 2}Al are polar intermetallics.« less

Characterization of complex carbide–silicide precipitates in a Ni–Cr–Mo–Fe–Si alloy modified by welding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, D., E-mail: dhb@ansto.gov.au; Davis, J.; Drew, M.

2015-07-15

Nickel based alloys of the type Hastelloy-N™ are ideal candidate materials for molten salt reactors, as well as for applications such as pressure vessels, due to their excellent resistance to creep, oxidation and corrosion. In this work, the authors have attempted to understand the effects of welding on the morphology, chemistry and crystal structure of the precipitates in the heat affected zone (HAZ) and the weld zone of a Ni–Cr–Mo–Fe–Si alloy similar to Hastelloy-N™ in composition, by using characterization techniques such as scanning and transmission electron microscopy. Two plates of a Ni–Cr–Mo–Fe–Si alloy GH-3535 were welded together using a TiGmore » welding process without filler material to achieve a joint with a curved molten zone with dendritic structure. It is evident that the primary precipitates have melted in the HAZ and re-solidified in a eutectic-like morphology, with a chemistry and crystal structure only slightly different from the pre-existing precipitates, while the surrounding matrix grains remained unmelted, except for the zones immediately adjacent to the precipitates. In the molten zone, the primary precipitates were fully melted and dissolved in the matrix, and there was enrichment of Mo and Si in the dendrite boundaries after solidification, and re-precipitation of the complex carbides/silicides at some grain boundaries and triple points. The nature of the precipitates in the molten zone varied according to the local chemical composition. - Graphical abstract: Display Omitted - Highlights: • Ni-based alloy with Cr, Mo, Si, Fe and C was welded, examined with SEM, EBSD, and TEM. • Original Ni{sub 2}(Mo,Cr){sub 4}(Si,C) carbides changed from equiaxed to lamellar shape in HAZ. • Composition and crystal structure remained almost unchanged in HAZ. • Original carbides changed to lamellar Ni{sub 3}(Mo,Cr){sub 3}(Si,C) in some cases in weld metal. • Precipitates were mostly incoherent, but semi-coherent in some cases in weld metal.« less

USSR and Eastern Europe Scientific Abstracts, Physics and Mathematics, Number 34

DTIC Science & Technology

1977-04-27

Russian abstract provided by the source] [Text] The relationship of duration and intensity of ultrashort pulses in a mode-locked ruby laser with Q...Excess charge carriers have been found to appear in pure Ge and Si crystals irradiated with short pulses from a C02 laser . The high purity and perfection...Illustrations 2; References 15: 8 Russian, 7 Western. USSR UDC 621.378.325 CONTROL OF DURATION OF ULTRASHORT PULSES IN MODE-LOCKED LASERS ZHURNAL

Microgravity protein crystallization

PubMed Central

McPherson, Alexander; DeLucas, Lawrence James

2015-01-01

Over the past 20 years a variety of technological advances in X-ray crystallography have shortened the time required to determine the structures of large macromolecules (i.e., proteins and nucleic acids) from several years to several weeks or days. However, one of the remaining challenges is the ability to produce diffraction-quality crystals suitable for a detailed structural analysis. Although the development of automated crystallization systems combined with protein engineering (site-directed mutagenesis to enhance protein solubility and crystallization) have improved crystallization success rates, there remain hundreds of proteins that either cannot be crystallized or yield crystals of insufficient quality to support X-ray structure determination. In an attempt to address this bottleneck, an international group of scientists has explored use of a microgravity environment to crystallize macromolecules. This paper summarizes the history of this international initiative along with a description of some of the flight hardware systems and crystallization results. PMID:28725714

Synthesis, crystal structure, optical, and electronic study of the new ternary thorium selenide Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prakash, Jai; Mesbah, Adel; ICSM, UMR 5257 CEA/CNRS/UM2/ENSCM, Site de Marcoule-Bât. 426, BP 17171, 30207 Bagnols-sur-Cèze cedex

2015-11-15

The compound Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} has been synthesized by solid-state methods at 1173 K. Its crystal structure features one-dimensional chains of {sup 1}{sub ∞}[Th(Se){sub 3}(Se{sub 2}){sub 2}{sup 6−}] separated by Ba{sup 2+} cations. Each Th atom in these chains is coordinated to two Se–Se single-bonded pairs and four Se atoms to give rise to a pseudooctahedral geometry around Th. The Th–Se distances are consistent with Th{sup 4+} and hence charge balance of Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} is achieved as 3×Ba{sup 2+}, 1×Th{sup 4+}, 3×Se{sup 2−}, and 2×Se{sub 2}{sup 2−}. From optical measurements the band gap of Ba{submore » 3}ThSe{sub 3}(Se{sub 2}){sub 2} is 1.96(2) eV. DFT calculations indicate that the compound is a semiconductor. - Graphical abstract: Local coordination environment of Th atoms in the Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} structure. - Highlights: • Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} has been synthesized by solid-state methods at 1173 K. • The structure features chains of {sup 1}{sub ∞}[Th(Se){sub 3}(Se{sub 2}){sub 2}{sup 6−}] separated by Ba{sup 2+} cations. • Ba{sub 3}ThSe{sub 3}(Se{sub 2}){sub 2} is a semiconductor with a band gap of 1.96(2) eV.« less

Structural and mutational analyses of the receptor binding domain of botulinum D/C mosaic neurotoxin: Insight into the ganglioside binding mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nuemket, Nipawan; Tanaka, Yoshikazu; Faculty of Advanced Life Science, Hokkaido University, Sapporo 060-0810

2011-07-29

Highlights: {yields} We determined the crystal structure of the receptor binding domain of BoNT in complex with 3'-sialyllactose. {yields} An electron density derived from the 3'-sialyllactose was confirmed at the cleft in the C-terminal subdomain. {yields} Alanine site-directed mutagenesis showed that GBS and GBL are important for ganglioside binding. {yields} A cell binding mechanism, which involves cooperative contribution of two sites, was proposed. -- Abstract: Clostridium botulinum type D strain OFD05, which produces the D/C mosaic neurotoxin, was isolated from cattle killed by the recent botulism outbreak in Japan. The D/C mosaic neurotoxin is the most toxic of the botulinummore » neurotoxins (BoNT) characterized to date. Here, we determined the crystal structure of the receptor binding domain of BoNT from strain OFD05 in complex with 3'-sialyllactose at a resolution of 3.0 A. In the structure, an electron density derived from the 3'-sialyllactose was confirmed at the cleft in the C-terminal subdomain. Alanine site-directed mutagenesis showed the significant contribution of the residues surrounding the cleft to ganglioside recognition. In addition, a loop adjoining the cleft also plays an important role in ganglioside recognition. In contrast, little effect was observed when the residues located around the surface previously identified as the protein receptor binding site in other BoNTs were substituted. The results of cell binding analysis of the mutants were significantly correlated with the ganglioside binding properties. Based on these observations, a cell binding mechanism of BoNT from strain OFD05 is proposed, which involves cooperative contribution of two ganglioside binding sites.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abdelbaky, Mohammed S.M.; Amghouz, Zakariae; Department of Materials Science and Metallurgical Engineering, University of Oviedo, Campus Universitario, 33203 Gijón

Novel metal phosphonate [CuLi(PPA)] [H{sub 3}PPA=3-phosphonopropionic acid] was synthesized hydrothermally and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, scanning electron microscopy, infrared spectroscopy, and thermogravimetric analysis. It crystallizes in the space group C2/c, with cell parameters a=21.617(2) Å, b=4.9269(2) Å, c=14.342(1) Å, β=132.3(2)°, and Z=8. Its framework is built up from a main trimer, acting as a secondary building unit (SBU), which is formed by vertex-shared between two (LiO{sub 4}) and one (Cu(1)O{sub 4}) polyhedra. These units repeat along b-axis forming infinite inorganic chains, these chains are in turn cross-linked by corner sharing with (Cu(2)O{sub 4}) polyhedra to producemore » inorganic layers lying in the bc-plane. The neighboring layers are connected through the PPA ligand, leading to a 3D pillared-layered structure. The topological analysis reveals that the compound exhibits 3,4,10-c net. Finally, magnetic susceptibility measurement of this compound over the temperature range of 2–300 K reveals the occurrence of weak antiferromagnetic intrachain interactions. - Graphical abstract: Hydrothermal synthesis and structural characterization of a novel lithium-copper phosphonate, formulated as [CuLi(PPA)] (H{sub 3}PPA=3-phosphonopropionic acid), have been reported. This compound has a 3D pillared-layered structure with 3,4,10-c net topology. The magnetic susceptibility data over the temperature range of 2–300 K reveals the occurrence of weak antiferromagnetic interactions. - Highlights: • Novel metal phosphonate, [CuLi(PPA)] (1), has been synthesized and characterized. • Compound 1 has a 3D pillared-layered structure with 3,4,10-c net topology. • Magnetic susceptibility data reveals the occurrence of weak antiferromagnetic interactions.« less

Crystal Structure of Manganese Lipoxygenase of the Rice Blast Fungus Magnaporthe oryzae*

PubMed Central

Wennman, Anneli; Oliw, Ernst H.; Karkehabadi, Saeid; Chen, Yang

2016-01-01

Lipoxygenases (LOX) are non-heme metal enzymes, which oxidize polyunsaturated fatty acids to hydroperoxides. All LOX belong to the same gene family, and they are widely distributed. LOX of animals, plants, and prokaryotes contain iron as the catalytic metal, whereas fungi express LOX with iron or with manganese. Little is known about metal selection by LOX and the adjustment of the redox potentials of their protein-bound catalytic metals. Thirteen three-dimensional structures of animal, plant, and prokaryotic FeLOX are available, but none of MnLOX. The MnLOX of the most important plant pathogen, the rice blast fungus Magnaporthe oryzae (Mo), was expressed in Pichia pastoris. Mo-MnLOX was deglycosylated, purified to homogeneity, and subjected to crystal screening and x-ray diffraction. The structure was solved by sulfur and manganese single wavelength anomalous dispersion to a resolution of 2.0 Å. The manganese coordinating sphere is similar to iron ligands of coral 8R-LOX and soybean LOX-1 but is not overlapping. The Asn-473 is positioned on a short loop (Asn-Gln-Gly-Glu-Pro) instead of an α-helix and forms hydrogen bonds with Gln-281. Comparison with FeLOX suggests that Phe-332 and Phe-525 might contribute to the unique suprafacial hydrogen abstraction and oxygenation mechanism of Mo-MnLOX by controlling oxygen access to the pentadiene radical. Modeling suggests that Arg-525 is positioned close to Arg-182 of 8R-LOX, and both residues likely tether the carboxylate group of the substrate. An oxygen channel could not be identified. We conclude that Mo-MnLOX illustrates a partly unique variation of the structural theme of FeLOX. PMID:26783260

High-pressure behaviour of Cs{sub 2}V{sub 3}O{sub 8} fresnoite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grzechnik, Andrzej, E-mail: grzechnik@xtal.rwth-aachen.de; Yeon, Jeongho; Zur Loye, Hans-Conrad

2016-06-15

Crystal structure of Cs{sub 2}V{sub 3}O{sub 8} fresnoite (P4bm, Z=2) has been studied using single-crystal X-ray diffraction in a diamond anvil cell to 8.6 GPa at room temperature. Cs{sub 2}V{sub 3}O{sub 8} undergoes a reversible first-order phase transition at about 4 GPa associated with anomalies in the pressure dependencies of the lattice parameters and unit-cell volume but without any symmetry change. Both structures consist of layers of corner-sharing V{sup 5+}O{sub 4} tetrahedra and V{sup 4+}O{sub 5} tetragonal pyramids separated by the Cs{sup +} cations located between the layers. At low pressures, the compression has little effect on the polarity ofmore » the structure. Above 4 GPa, the pseudosymmetry with respect to the corresponding centrosymmetric space group P4/mbm abruptly increases. The effects of external pressure and of the A{sup +} cation substitution in the vanadate fresnoites A{sub 2}V{sub 3}O{sub 8} (A{sup +}: K{sup +}, Rb{sup +}, NH{sub 4}{sup +}, Cs{sup +}) are discussed. - Graphical abstract: Non-centrosymmetric Cs{sub 2}V{sub 3}O{sub 8} undergoes a reversible first-order phase transition at about 4 GPa associated with an abrupt change of the pseudosymmetry with respect to the centrosymmetric space group P4/mbm. Display Omitted - Highlights: • High-pressure behaviour of vanadate fresnoites depends on alkali metal cations. • The size of the alkali metal cation determines whether the high-pressure phase is centrosymmetric. • No incommensurate structures are observed upon compression.« less

Structural basis for high substrate-binding affinity and enantioselectivity of 3-quinuclidinone reductase AtQR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hou, Feng; Miyakawa, Takuya; Kataoka, Michihiko

2014-04-18

Highlights: • Crystal structure of AtQR has been determined at 1.72 Å. • NADH binding induces the formation of substrate binding site. • AtQR possesses a conserved hydrophobic wall for stereospecific binding of substrate. • Additional Glu197 residue is critical to the high binding affinity. - Abstract: (R)-3-Quinuclidinol, a useful compound for the synthesis of various pharmaceuticals, can be enantioselectively produced from 3-quinuclidinone by 3-quinuclidinone reductase. Recently, a novel NADH-dependent 3-quinuclidionone reductase (AtQR) was isolated from Agrobacterium tumefaciens, and showed much higher substrate-binding affinity (>100 fold) than the reported 3-quinuclidionone reductase (RrQR) from Rhodotorula rubra. Here, we report the crystalmore » structure of AtQR at 1.72 Å. Three NADH-bound protomers and one NADH-free protomer form a tetrameric structure in an asymmetric unit of crystals. NADH not only acts as a proton donor, but also contributes to the stability of the α7 helix. This helix is a unique and functionally significant part of AtQR and is related to form a deep catalytic cavity. AtQR has all three catalytic residues of the short-chain dehydrogenases/reductases family and the hydrophobic wall for the enantioselective reduction of 3-quinuclidinone as well as RrQR. An additional residue on the α7 helix, Glu197, exists near the active site of AtQR. This acidic residue is considered to form a direct interaction with the amine part of 3-quinuclidinone, which contributes to substrate orientation and enhancement of substrate-binding affinity. Mutational analyses also support that Glu197 is an indispensable residue for the activity.« less

Lead(II) coordination polymers based on rigid-flexible 3,5-bis-oxyacetate-benzoic acid: Structural transition driven by temperature control

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yong-Qiang, E-mail: chenjzxy@126.com; Tian, Yuan

2017-03-15

Three Pb(II) complexes ([Pb{sub 3}(BOABA){sub 2}(H{sub 2}O)]·H{sub 2}O){sub n} (1), ([Pb{sub 4}(BOABA){sub 2}(µ{sub 4}-O)(H{sub 2}O){sub 2}]·H{sub 2}O){sub n} (2), and [Pb{sub 3}(BOABA){sub 2}(H{sub 2}O)]{sub n} (3) (H{sub 3}BOABA=3,5-bis-oxyacetate-benzoic acid) were obtained under the same reaction systems with different temperatures. Complexes 1 and 2 are two dimensional (2D) networks based on Pb-BOABA chains and Pb{sub 4}(µ{sub 4}-O)(COO){sub 6} SBUs, respectively. Complex 3 presents an interesting three dimensional (3D) framework, was obtained by increasing the reaction temperature. Structural transition of the crystallization products is largely dependent on the reaction temperature. Moreover, the fluorescence properties of complexes 1–3 have been investigated. - Graphicalmore » abstract: Three Pb(II) coordination polymers were obtained under the same reaction systems with different temperatures. Both of complexes 1 and 2 are 2D network. 3 presents a 3D framework based on Pb–O–C rods SBUs. The 2D to 3D structures transition between three complexes was achieved successfully by temperature control. - Highlights: • Three Pb(II) complexes were obtained under the same reaction systems with different temperatures. • Structural transition of the crystallization products is largely dependent on the reaction temperature. • The luminescence properties studies reveal that three complexes exhibit yellow fluorescence emission behavior, which might be good candidates for obtaining photoluminescent materials.« less

Ionic‐Liquid‐Assisted Microwave Synthesis of Solid Solutions of Sr1−xBaxSnO3 Perovskite for Photocatalytic Applications

PubMed Central

Alammar, Tarek; Slowing, Igor I.; Anderegg, Jim

2017-01-01

Abstract Nanocrystalline Sr1−xBaxSnO3 (x=0, 0.2, 0.4, 0.8, 1) perovskite photocatalysts were prepared by microwave synthesis in an ionic liquid (IL) and subsequent heat‐treatment. The influence of the Sr/Ba substitution on the structure, crystallization, morphology, and photocatalytic efficiency was investigated and the samples were fully characterized. On the basis of X‐ray diffraction results, as the Ba content in the SrSnO3 lattice increases, a symmetry increase was observed from the orthorhombic perovskite structure for SrSnO3 to the cubic BaSnO3 structure. The analysis of the sample morphology by SEM reveals that the Sr1−xBaxSnO3 samples favor the formation of nanorods (500 nm–5 μm in diameter and several micrometers long). The photophysical properties were examined by UV/Vis diffuse reflectance spectroscopy. The band gap decreases from 3.85 to 3.19 eV with increasing Ba2+ content. Furthermore, the photocatalytic properties were evaluated for the hydroxylation of terephthalic acid (TA). The order of the activities for TA hydroxylation was Sr0.8Ba0.2SnO3>SrSnO3>BaSnO3>Sr0.6Ba0.4SnO3>Sr0.2Ba0.8SnO3. The highest photocatalytic activity was observed for Sr0.8Ba0.2SnO3, and this can be attributed to the synergistic impacts of the modification of the crystal structure and morphology, the relatively large surface area associated with the small crystallite size, and the suitable band gap and band‐edge position. PMID:28589568

Ultratight crystal packing of a 10 kDa protein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trillo-Muyo, Sergio; Jasilionis, Andrius; Domagalski, Marcin J.

2013-03-01

The crystal structure of the C-terminal domain of a putative U32 peptidase from G. thermoleovorans is reported; it is one of the most tightly packed protein structures reported to date. While small organic molecules generally crystallize forming tightly packed lattices with little solvent content, proteins form air-sensitive high-solvent-content crystals. Here, the crystallization and full structure analysis of a novel recombinant 10 kDa protein corresponding to the C-terminal domain of a putative U32 peptidase are reported. The orthorhombic crystal contained only 24.5% solvent and is therefore among the most tightly packed protein lattices ever reported.

A Two-Tailed Phosphopeptide Crystallizes to Form a Lamellar Structure.

PubMed

Pellach, Michal; Mondal, Sudipta; Harlos, Karl; Mance, Deni; Baldus, Marc; Gazit, Ehud; Shimon, Linda J W

2017-03-13

The crystal structure of a designed phospholipid-inspired amphiphilic phosphopeptide at 0.8 Å resolution is presented. The phosphorylated β-hairpin peptide crystallizes to form a lamellar structure that is stabilized by intra- and intermolecular hydrogen bonding, including an extended β-sheet structure, as well as aromatic interactions. This first reported crystal structure of a two-tailed peptidic bilayer reveals similarities in thickness to a typical phospholipid bilayer. However, water molecules interact with the phosphopeptide in the hydrophilic region of the lattice. Additionally, solid-state NMR was used to demonstrate correlation between the crystal structure and supramolecular nanostructures. The phosphopeptide was shown to self-assemble into semi-elliptical nanosheets, and solid-state NMR provides insight into the self-assembly mechanisms. This work brings a new dimension to the structural study of biomimetic amphiphilic peptides with determination of molecular organization at the atomic level. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio study of structural and mechanical property of solid molecular hydrogens

NASA Astrophysics Data System (ADS)

Ye, Yingting; Yang, Li; Yang, Tianle; Nie, Jinlan; Peng, Shuming; Long, Xinggui; Zu, Xiaotao; Du, Jincheng

2015-06-01

Ab initio calculations based on density functional theory (DFT) were performed to investigate the structural and the elastic properties of solid molecular hydrogens (H2). The influence of molecular axes of H2 on structural relative stabilities of hexagonal close-packed (hcp) and face-centered cubic (fcc) structured hydrogen molecular crystals were systematically investigated. Our results indicate that for hcp structures, disordered hydrogen molecule structure is more stable, while for fcc structures, Pa3 hydrogen molecular crystal is most stable. The cohesive energy of fcc H2 crystal was found to be lower than hcp. The mechanical properties of fcc and hcp hydrogen molecular crystals were obtained, with results consistent with previous theoretical calculations. In addition, the effects of zero point energy (ZPE) and van der Waals (vdW) correction on the cohesive energy and the stability of hydrogen molecular crystals were systematically studied and discussed.

Stochastic generation of complex crystal structures combining group and graph theory with application to carbon

NASA Astrophysics Data System (ADS)

Shi, Xizhi; He, Chaoyu; Pickard, Chris J.; Tang, Chao; Zhong, Jianxin

2018-01-01

A method is introduced to stochastically generate crystal structures with defined structural characteristics. Reasonable quotient graphs for symmetric crystals are constructed using a random strategy combined with space group and graph theory. Our algorithm enables the search for large-size and complex crystal structures with a specified connectivity, such as threefold sp2 carbons, fourfold sp3 carbons, as well as mixed sp2-sp3 carbons. To demonstrate the method, we randomly construct initial structures adhering to space groups from 75 to 230 and a range of lattice constants, and we identify 281 new sp3 carbon crystals. First-principles optimization of these structures show that most of them are dynamically and mechanically stable and are energetically comparable to those previously proposed. Some of the new structures can be considered as candidates to explain the experimental cold compression of graphite.

Life in the fast lane for protein crystallization and X-ray crystallography

NASA Technical Reports Server (NTRS)

Pusey, Marc L.; Liu, Zhi-Jie; Tempel, Wolfram; Praissman, Jeremy; Lin, Dawei; Wang, Bi-Cheng; Gavira, Jose A.; Ng, Joseph D.

2005-01-01

The common goal for structural genomic centers and consortiums is to decipher as quickly as possible the three-dimensional structures for a multitude of recombinant proteins derived from known genomic sequences. Since X-ray crystallography is the foremost method to acquire atomic resolution for macromolecules, the limiting step is obtaining protein crystals that can be useful of structure determination. High-throughput methods have been developed in recent years to clone, express, purify, crystallize and determine the three-dimensional structure of a protein gene product rapidly using automated devices, commercialized kits and consolidated protocols. However, the average number of protein structures obtained for most structural genomic groups has been very low compared to the total number of proteins purified. As more entire genomic sequences are obtained for different organisms from the three kingdoms of life, only the proteins that can be crystallized and whose structures can be obtained easily are studied. Consequently, an astonishing number of genomic proteins remain unexamined. In the era of high-throughput processes, traditional methods in molecular biology, protein chemistry and crystallization are eclipsed by automation and pipeline practices. The necessity for high-rate production of protein crystals and structures has prevented the usage of more intellectual strategies and creative approaches in experimental executions. Fundamental principles and personal experiences in protein chemistry and crystallization are minimally exploited only to obtain "low-hanging fruit" protein structures. We review the practical aspects of today's high-throughput manipulations and discuss the challenges in fast pace protein crystallization and tools for crystallography. Structural genomic pipelines can be improved with information gained from low-throughput tactics that may help us reach the higher-bearing fruits. Examples of recent developments in this area are reported from the efforts of the Southeast Collaboratory for Structural Genomics (SECSG).

Life in the Fast Lane for Protein Crystallization and X-Ray Crystallography

NASA Technical Reports Server (NTRS)

Pusey, Marc L.; Liu, Zhi-Jie; Tempel, Wolfram; Praissman, Jeremy; Lin, Dawei; Wang, Bi-Cheng; Gavira, Jose A.; Ng, Joseph D.

2004-01-01

The common goal for structural genomic centers and consortiums is to decipher as quickly as possible the three-dimensional structures for a multitude of recombinant proteins derived from known genomic sequences. Since X-ray crystallography is the foremost method to acquire atomic resolution for macromolecules, the limiting step is obtaining protein crystals that can be useful of structure determination. High-throughput methods have been developed in recent years to clone, express, purify, crystallize and determine the three-dimensional structure of a protein gene product rapidly using automated devices, commercialized kits and consolidated protocols. However, the average number of protein structures obtained for most structural genomic groups has been very low compared to the total number of proteins purified. As more entire genomic sequences are obtained for different organisms from the three kingdoms of life, only the proteins that can be crystallized and whose structures can be obtained easily are studied. Consequently, an astonishing number of genomic proteins remain unexamined. In the era of high-throughput processes, traditional methods in molecular biology, protein chemistry and crystallization are eclipsed by automation and pipeline practices. The necessity for high rate production of protein crystals and structures has prevented the usage of more intellectual strategies and creative approaches in experimental executions. Fundamental principles and personal experiences in protein chemistry and crystallization are minimally exploited only to obtain "low-hanging fruit" protein structures. We review the practical aspects of today s high-throughput manipulations and discuss the challenges in fast pace protein crystallization and tools for crystallography. Structural genomic pipelines can be improved with information gained from low-throughput tactics that may help us reach the higher-bearing fruits. Examples of recent developments in this area are reported from the efforts of the Southeast Collaboratory for Structural Genomics (SECSG).

Theoretical exploration of various lithium peroxide crystal structures in a Li-air battery

DOE PAGES

Lau, Kah; Qiu, Dantong; Luo, Xiangyi; ...

2015-01-14

We describe a series of metastable Li₂O₂ crystal structures involving different orientations and displacements of the O₂²⁻ peroxy ions based on the known Li₂O₂ crystal structure. Within the vicinity of the chemical potential ΔG ~ 0.20 eV/Li from the thermodynamic ground state of the Li₂O₂ crystal structure (i.e., Föppl structure), all of these newly found metastable Li₂O₂ crystal structures are found to be insulating and high-k materials, and they have a common unique signature of an O₂²⁻ O-O vibration mode (ω ~ 799–865 cm⁻¹), which is in the range of that commonly observed in Li-air battery experiments, regardless of themore » random O₂²⁻ orientations and the symmetry in the crystal lattice. From XRD patterns analysis, the commercially available Li₂O₂ powder is confirmed to be the thermodynamic ground state Föppl-like structure. However, for Li₂O₂ compounds that are grown electrochemically under the environment of Li-O₂ cells, we found that the XRD patterns alone are not sufficient for structural identification of these metastable Li₂O₂ crystalline phases due to the poor crystallinity of the sample. In addition, the commonly known Raman signal of O₂²⁻ vibration mode is also found to be insufficient to validate the possible existence of these newly predicted Li₂O₂ crystal structures, as all of them similarly share the similar O₂²⁻ vibration mode. However considering that the discharge voltage in most Li-O₂ cells are typically several tenths of an eV below the thermodynamic equilibrium for the formation of ground state Föppl structure, the formation of these metastable Li₂O₂ crystal structures appears to be thermodynamically feasible.« less

Crystal Structure and Crystal Chemistry of Some Common REE Minerals and Nanpingite

NASA Astrophysics Data System (ADS)

Ni, Yunxiang

1995-01-01

Part I. Crystal structure and crystal chemistry of fluorocarbonate minerals. The crystal structure of bastnasite-(Ce) have been solved in P-62c and refined to R = 0.018. The structure is composed of (001) (CeF) layers interspersed with (CO_3) layers in a 1:1 ratio. The Ce atom is coordinated in rm CeO_6F_3 polyhedra. The atomic arrangement of synchysite-(Ce) has been solved and refined to R = 0.036 with a monoclinic space group C2/c. It possesses a (001) layer structure, with layers of (Ca) and (CeF) separated by layers of carbonate groups. The layers stack in a manner analogous to C2/c muscovite. Polytypism similar to the micas may exist in synchysite. The crystal structures of cordylite-(Ce) have been solved in P6 _3/mmc and refined to R = 0.023. The structure and chemical formula are different from those deduced by Oftedal. The formula is rm MBaCe_2(CO _3)_4F, where M is rm Na^+, Ca^{2+}_{1/2 }+ O_{1/2}, or any solution. The presence of (NaF) layer in the structure is the key difference from the Oftedal's structure. This redefinition of the chemical formula and crystal structure of cordylite will be proposed to IMA-CNMMN. Part II. Crystal structure and crystal chemistry of monazite-xenotime series. Monazite is monoclinic, P2 _1/n, and xenotime is isostructural with zircon (I4_1/amd). Both atomic arrangements are based on (001) chains of intervening phosphate tetrahedra and RE polyhedra, with a REO_8 polyhedron in xenotime that accommodates HRE (Tb - Lu) and a REO_9 polyhedron in monazite that preferentially incorporates LRE (La - Gd). As the structure "transforms" from xenotime to monazite, the crystallographic properties are comparable along the (001) chains, with structural adjustments of 2.2 A along (010) to accommodate the different size RE atoms. Part III. Crystal structure of nanpingite-2M _2, the Cs end-member of muscovite. The crystal structure of nanpingite has been refined to R = 0.058. Compared to K^+ in muscovite, the largest interlayer Cs^+ in nanpingite increases (001) separation between adjacent 2:1 layers, but has little effect on the dimensions in (001). The existence of rare 2M_2 polytype in nanpingite is attributed to this large layer separation, which minimizes the repulsion of the superimposed (along (001)) basal oxygens in neighboring tetrahedral layers.

Inorganic Crystal Structure Database (ICSD) and Standardized Data and Crystal Chemical Characterization of Inorganic Structure Types (TYPIX)—Two Tools for Inorganic Chemists and Crystallographers

PubMed Central

Fluck, Ekkehard

1996-01-01

The two databases ICSD and TYPIX are described. ICSD is a comprehensive compilation of crystal structure data of inorganic compounds (about 39 000 entries). TYPIX contains 3600 critically evaluated data sets representative of structure types formed by inorganic compounds. PMID:27805158

Recent advances and progress in photonic crystal-based gas sensors

NASA Astrophysics Data System (ADS)

Goyal, Amit Kumar; Sankar Dutta, Hemant; Pal, Suchandan

2017-05-01

This review covers the recent progress made in the photonic crystal-based sensing technology for gas sensing applications. Photonic crystal-based sensing has tremendous potential because of its obvious advantages in sensitivity, stability, miniaturisation, portability, online use, remote monitoring etc. Several 1D and 2D photonic crystal structures including photonic crystal waveguides and cavities for gas sensing applications have been discussed in this review. For each kind of photonic crystal structure, the novelty, measurement principle and their respective gas sensing properties are presented. The reported works and the corresponding results predict the possibility to realize a commercially viable miniaturized and highly sensitive photonic crystal-based optical gas sensor having flexibility in the structure of ultra-compact size with excellent sensing properties.

Structural Color Patterns by Electrohydrodynamic Jet Printed Photonic Crystals.

PubMed

Ding, Haibo; Zhu, Cun; Tian, Lei; Liu, Cihui; Fu, Guangbin; Shang, Luoran; Gu, Zhongze

2017-04-05

In this work, we demonstrate the fabrication of photonic crystal patterns with controllable morphologies and structural colors utilizing electrohydrodynamic jet (E-jet) printing with colloidal crystal inks. The final shape of photonic crystal units is controlled by the applied voltage signal and wettability of the substrate. Optical properties of the structural color patterns are tuned by the self-assembly of the silica nanoparticle building blocks. Using this direct printing technique, it is feasible to print customized functional patterns composed of photonic crystal dots or photonic crystal lines according to relevant printing mode and predesigned tracks. This is the first report for E-jet printing with colloidal crystal inks. Our results exhibit promising applications in displays, biosensors, and other functional devices.

Phase equilibria in the La–Mg–Ge system at 500 °C and crystal structure of the new ternary compounds La{sub 11}Mg{sub 2}Ge{sub 7} and LaMg{sub 3−x}Ge{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Negri, S., E-mail: serena.denegri@unige.it; Solokha, P.; Skrobańska, M.

2014-10-15

The whole 500 °C isothermal section of the La–Mg–Ge ternary system was constructed. The existence and crystal structure of three ternary compounds were confirmed: La{sub 2+x}Mg{sub 1−x}Ge{sub 2} (τ{sub 2}, P4/mbm, tP10–Mo{sub 2}FeB{sub 2}, 0≤x≤0.25), La{sub 4}Mg{sub 5}Ge{sub 6} (τ{sub 3}, Cmc2{sub 1}, oS60–Gd{sub 4}Zn{sub 5}Ge{sub 6}) and La{sub 4}Mg{sub 7}Ge{sub 6} (τ{sub 4}, C2/m, mS34, own structure type). Five novel compounds were identified and structurally characterized: La{sub 11}Mg{sub 2}Ge{sub 7} (τ{sub 1}, P4{sub 2}/ncm, tP88-8, own structure type, a=1.21338(5), c=1.57802(6) nm), LaMg{sub 3−x}Ge{sub 2} (τ{sub 5}, P3{sup ¯}1c, hP34-0.44, own structure type, x=0.407(5), a=0.78408(4), c=1.45257(7) nm), La{sub 6}Mg{sub 23}Gemore » (τ{sub 6}, Fm3{sup ¯}m, cF120–Zr{sub 6}Zn{sub 23}Si, a=1.46694(6) nm), La{sub 4}MgGe{sub 10−x} (τ{sub 7}, x=0.37(1), C2/m, mS60-1.46, own structure type, a=0.88403(8), b=0.86756(8), c=1.7709(2) nm, β=97.16°(1) and La{sub 2}MgGe{sub 6} (τ{sub 8}, Cmce, oS72–Ce{sub 2}(Ga{sub 0.1}Ge{sub 0.9}){sub 7}, a=0.8989(2), b=0.8517(2), c=2.1064(3) nm). Disordering phenomena were revealed in several La–Mg–Ge phases in terms of partially occupied sites. The crystal structures of La{sub 11}Mg{sub 2}Ge{sub 7} and LaMg{sub 3−x}Ge{sub 2} are discussed in details. The latter is a √3a×√3a×2c superstructure of the LaLi{sub 3}Sb{sub 2} structure type; the symmetry reduction scheme is shown in the Bärnighausen formalism terms. - Graphical abstract: La–Mg–Ge isothermal section at 500 °C and group–subgroup relation between the LaLi{sub 3}Sb{sub 2} (parent type) and LaMg{sub 3−x}Ge{sub 2} (derivative) structures. - Highlights: • Novel La−Mg−Ge compounds structure determination from X-ray single crystal data. • Disordering phenomena as common features of the studied germanides. • Bärnighausen formalism as a useful tool for accurate structure determination. • Full isothermal section of the La–Mg–Ge ternary system at 500 °C.« less

Simultaneous presence of (Si{sub 3}O{sub 10}){sup 8−} and (Si{sub 2}O{sub 7}){sup 6−} groups in new synthetic mixed sorosilicates: BaY{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}) and isotypic compounds, studied by single-crystal X-ray diffraction, Raman spectroscopy and DFT calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wierzbicka-Wieczorek, Maria, E-mail: maria.wierzbicka-wieczorek@uni-jena.de; Többens, Daniel M.; Kolitsch, Uwe

2013-11-15

Three new, isotypic silicate compounds, BaY{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}), SrYb{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}) and SrSc{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}), were synthesized using high-temperature flux growth techniques, and their crystal structures were solved from single-crystal X-ray intensity data: monoclinic, P2{sub 1}/m, with a=5.532(1)/5.469(1)/5.278(1), b=19.734(4)/19.447(4)/19.221(4), c=6.868(1)/6.785(1)/6.562(1) Å, β=106.53(3)/106.20(3)/106.50(3)°, V=718.8(2)/693.0(2)/638.3(2) Å{sup 3}, R(F)=0.0225/0.0204/0.0270, respectively. The topology of the novel structure type contains isolated horseshoe-shaped Si{sub 3}O{sub 10} groups (Si–Si–Si=93.15–95.98°), Si{sub 2}O{sub 7} groups (Si–O{sub bridge}–Si=180°, symmetry-restricted) and edge-sharing M(1)O{sub 6} and M(2)O{sub 6} octahedra. Single-crystal Raman spectra of the title compounds were measured and compared with Raman spectroscopicmore » data of chemically and topologically related disilicates and trisilicates, including BaY{sub 2}(Si{sub 3}O{sub 10}) and SrY{sub 2}(Si{sub 3}O{sub 10}). The band assignments are supported by additional theoretical calculation of Raman vibrations by DFT methods. - Graphical abstract: View of BaY{sub 4}(Si{sub 2}O{sub 7})(Si{sub 3}O{sub 10}) along [100], showing zigzag chains and the tri- and disilicate groups. The unit cell is outlined. Display Omitted - Highlights: • We report a novel interesting crystal structure type for mixed sorosilicates containing Y, Yb, and Sc. • Synthesis of such mixed sorosilicates is possible by a high-temperature flux-growth technique. • Calculation of Raman vibrations by advanced DFT methods allows a considerably improved interpretation of measured Raman spectra.« less

Powder diffraction and crystal structure prediction identify four new coumarin polymorphs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shtukenberg, Alexander G.; Zhu, Qiang; Carter, Damien J.

Coumarin, a simple, commodity chemical isolated from beans in 1820, has, to date, only yielded one solid state structure. Here, we report a rich polymorphism of coumarin grown from the melt. Four new metastable forms were identified and their crystal structures were solved using a combination of computational crystal structure prediction algorithms and X-ray powder diffraction. With five crystal structures, coumarin has become one of the few rigid molecules showing extensive polymorphism at ambient conditions. We demonstrate the crucial role of advanced electronic structure calculations including many-body dispersion effects for accurate ranking of the stability of coumarin polymorphs and themore » need to account for anharmonic vibrational contributions to their free energy. As such, coumarin is a model system for studying weak intermolecular interactions, crystallization mechanisms, and kinetic effects.« less

Powder diffraction and crystal structure prediction identify four new coumarin polymorphs

DOE PAGES

Shtukenberg, Alexander G.; Zhu, Qiang; Carter, Damien J.; ...

2017-05-15

Coumarin, a simple, commodity chemical isolated from beans in 1820, has, to date, only yielded one solid state structure. Here, we report a rich polymorphism of coumarin grown from the melt. Four new metastable forms were identified and their crystal structures were solved using a combination of computational crystal structure prediction algorithms and X-ray powder diffraction. With five crystal structures, coumarin has become one of the few rigid molecules showing extensive polymorphism at ambient conditions. We demonstrate the crucial role of advanced electronic structure calculations including many-body dispersion effects for accurate ranking of the stability of coumarin polymorphs and themore » need to account for anharmonic vibrational contributions to their free energy. As such, coumarin is a model system for studying weak intermolecular interactions, crystallization mechanisms, and kinetic effects.« less

Crystal structure, spectral, thermal and dielectric studies of a new zinc benzoate single crystal

NASA Astrophysics Data System (ADS)

Bijini, B. R.; Prasanna, S.; Deepa, M.; Nair, C. M. K.; Rajendra Babu, K.

2012-11-01

Single crystals of zinc benzoate with a novel structure were grown in gel media. Sodium metasilicate of gel density 1.04 g/cc at pH 6 was employed to yield transparent single crystals. The crystal structure of the compound was ascertained by single crystal X-ray diffractometry. It was noted that the crystal belongs to monoclinic system with space group P21/c with unit cell parameters a = 10.669(1) Å, b = 12.995(5) Å, c = 19.119(3) Å, and β = 94.926(3)°. The crystal was seen to possess a linear polymeric structure along b-axis; with no presence of coordinated or lattice water. CHN analysis established the stoichiometric composition of the crystal. The existence of functional groups present in the single crystal system was confirmed by FT-IR studies. The thermal characteristic of the sample was analysed by TGA-DTA techniques, and the sample was found to be thermally stable up to 280 °C. The kinetic and thermodynamic parameters were also determined. UV-Vis spectroscopy corroborated the transparency of the crystal and revealed the optical band gap to be 4 eV. Dielectric studies showed decrease in the dielectric constant of the sample with increase in frequency.

Construction of nanostructures for selective lithium ion conduction using self-assembled molecular arrays in supramolecular solids

NASA Astrophysics Data System (ADS)

Moriya, Makoto

2017-12-01

In the development of innovative molecule-based materials, the identification of the structural features in supramolecular solids and the understanding of the correlation between structure and function are important factors. The author investigated the development of supramolecular solid electrolytes by constructing ion conduction paths using a supramolecular hierarchical structure in molecular crystals because the ion conduction path is an attractive key structure due to its ability to generate solid-state ion diffusivity. The obtained molecular crystals exhibited selective lithium ion diffusion via conduction paths consisting of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and small molecules such as ether or amine compounds. In the present review, the correlation between the crystal structure and ion conductivity of the obtained molecular crystals is addressed based on the systematic structural control of the ionic conduction paths through the modification of the component molecules. The relationship between the crystal structure and ion conductivity of the molecular crystals provides a guideline for the development of solid electrolytes based on supramolecular solids exhibiting rapid and selective lithium ion conduction.

Probing the crystal structure landscape by doping: 4-bromo, 4-chloro and 4-methylcinnamic acids.

PubMed

Desiraju, Gautam R; Chakraborty, Shaunak; Joseph, Sumy

2018-06-11

Accessing the data points in the crystal structure landscape of a molecule is a challenging task, either experimentally or computationally. We have charted the crystal structure landscape of 4-bromocinnamic acid (4BCA) experimentally and computationally: experimental doping is achieved with 4-methylcinnamic acid (4MCA) to obtain new crystal structures; computational doping is performed with 4-chlorocinnamic acid (4CCA) as a model system, because of the difficulties associated in parameterizing the Br-atom. The landscape of 4CCA is explored experimentally in turn, also by doping it with 4MCA, and is found to bear a close resemblance to the landscape of 4BCA, justifying the ready miscibility of these two halogenated cinnamic acids to form solid solutions without any change in crystal structure. In effect, 4MCA, 4CCA and 4BCA form a commutable group of crystal structures, which may be realized experimentally or computationally, and constitute the landscape. Unlike the results obtained by Kitaigorodskii and others, all but two of the multiple solid solutions obtained in the methyl-doping experiments take structures that are different from the hitherto observed crystal forms of the parent compounds. Even granted that the latter might be inherently polymorphic, this unusual observation provokes the suggestion that solid solution formation may be used to probe the crystal structure landscape. The influence of pi...pi interactions, weak hydrogen bonds and halogen bonds in directing the formation of these new structures is also seen. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

2011 Nanoelectronic Devices for Defense & Security (NANO-DDS) Conference Held in Brooklyn, New York on August 29-September 1, 2011. Technical Program and Abstract Digest

DTIC Science & Technology

2011-08-01

challenges in new design methodologies . Particular examples involve an in-circuit functional timing testing of systems with millions of cores. I...TECHNIQUES Chair: Dwight Woolard, U.S. Army Research Office (ARO) 8:40-9:05 EXPERIMENTAL DESIGN OF SINGLE-CRYSTAL DNA FOR THZ SPECTROSCOPY...Detection Based Techniques EXPERIMENTAL DESIGN OF SINGLE-CRYSTAL DNA FOR THZ SPECTROSCOPY E. R. Brown, M.L. Norton, M. Rahman, W. Zhang Wright

Functional materials discovery using energy-structure-function maps

NASA Astrophysics Data System (ADS)

Pulido, Angeles; Chen, Linjiang; Kaczorowski, Tomasz; Holden, Daniel; Little, Marc A.; Chong, Samantha Y.; Slater, Benjamin J.; McMahon, David P.; Bonillo, Baltasar; Stackhouse, Chloe J.; Stephenson, Andrew; Kane, Christopher M.; Clowes, Rob; Hasell, Tom; Cooper, Andrew I.; Day, Graeme M.

2017-03-01

Molecular crystals cannot be designed in the same manner as macroscopic objects, because they do not assemble according to simple, intuitive rules. Their structures result from the balance of many weak interactions, rather than from the strong and predictable bonding patterns found in metal-organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail. Here we combine computational crystal structure prediction and property prediction to build energy-structure-function maps that describe the possible structures and properties that are available to a candidate molecule. Using these maps, we identify a highly porous solid, which has the lowest density reported for a molecular crystal so far. Both the structure of the crystal and its physical properties, such as methane storage capacity and guest-molecule selectivity, are predicted using the molecular structure as the only input. More generally, energy-structure-function maps could be used to guide the experimental discovery of materials with any target function that can be calculated from predicted crystal structures, such as electronic structure or mechanical properties.

Functional materials discovery using energy-structure-function maps.

PubMed

Pulido, Angeles; Chen, Linjiang; Kaczorowski, Tomasz; Holden, Daniel; Little, Marc A; Chong, Samantha Y; Slater, Benjamin J; McMahon, David P; Bonillo, Baltasar; Stackhouse, Chloe J; Stephenson, Andrew; Kane, Christopher M; Clowes, Rob; Hasell, Tom; Cooper, Andrew I; Day, Graeme M

2017-03-30

Molecular crystals cannot be designed in the same manner as macroscopic objects, because they do not assemble according to simple, intuitive rules. Their structures result from the balance of many weak interactions, rather than from the strong and predictable bonding patterns found in metal-organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail. Here we combine computational crystal structure prediction and property prediction to build energy-structure-function maps that describe the possible structures and properties that are available to a candidate molecule. Using these maps, we identify a highly porous solid, which has the lowest density reported for a molecular crystal so far. Both the structure of the crystal and its physical properties, such as methane storage capacity and guest-molecule selectivity, are predicted using the molecular structure as the only input. More generally, energy-structure-function maps could be used to guide the experimental discovery of materials with any target function that can be calculated from predicted crystal structures, such as electronic structure or mechanical properties.

Alignment of crystal orientations of the multi-domain photonic crystals in Parides sesostris wing scales

PubMed Central

Yoshioka, S.; Fujita, H.; Kinoshita, S.; Matsuhana, B.

2014-01-01

It is known that the wing scales of the emerald-patched cattleheart butterfly, Parides sesostris, contain gyroid-type photonic crystals, which produce a green structural colour. However, the photonic crystal is not a single crystal that spreads over the entire scale, but it is separated into many small domains with different crystal orientations. As a photonic crystal generally has band gaps at different frequencies depending on the direction of light propagation, it seems mysterious that the scale is observed to be uniformly green under an optical microscope despite the multi-domain structure. In this study, we have carefully investigated the structure of the wing scale and discovered that the crystal orientations of different domains are not perfectly random, but there is a preferred crystal orientation that is aligned along the surface normal of the scale. This finding suggests that there is an additional factor during the developmental process of the microstructure that regulates the crystal orientation. PMID:24352678

Crystal-to-Crystal Transition of Ultrasoft Colloids under Shear

NASA Astrophysics Data System (ADS)

Ruiz-Franco, J.; Marakis, J.; Gnan, N.; Kohlbrecher, J.; Gauthier, M.; Lettinga, M. P.; Vlassopoulos, D.; Zaccarelli, E.

2018-02-01

Ultrasoft colloids typically do not spontaneously crystallize, but rather vitrify, at high concentrations. Combining in situ rheo-small-angle-neutron-scattering experiments and numerical simulations we show that shear facilitates crystallization of colloidal star polymers in the vicinity of their glass transition. With increasing shear rate well beyond rheological yielding, a transition is found from an initial bcc-dominated structure to an fcc-dominated one. This crystal-to-crystal transition is not accompanied by intermediate melting but occurs via a sudden reorganization of the crystal structure. Our results provide a new avenue to tailor colloidal crystallization and the crystal-to-crystal transition at the molecular level by coupling softness and shear.

Crystal growth, structure analysis and characterisation of 2 - (1, 3 - dioxoisoindolin - 2 - yl) acetic acid single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sankari, R. Siva, E-mail: sivasankari.sh@act.edu.in; Perumal, Rajesh Narayana

2014-04-24

Single crystal of dielectric material 2 - (1, 3 - dioxoisoindolin - 2 - yl) acetic acid has been grown by slow evaporation solution growth method. The grown crystal was harvested in 25 days. The crystal structure was analyzed by Single crystal X - ray diffraction. UV-vis-NIR analysis was performed to examine the optical property of the grown crystal. The thermal property of the grown crystal was studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The dielectric measurements were carried out and the dielectric constant was calculated and plotted at all frequencies.

Structural and photoluminescence investigations of Sm{sup 3+} doped BaY{sub 2}ZnO{sub 5} nanophosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chahar, Sangeeta; Taxak, V.B.; Dalal, Mandeep

2016-05-15

Highlights: • BaY{sub 2(1−x)}Sm{sub 2x}ZnO{sub 5} nanophosphors have been synthesized via solution combustion. • The nanophosphors have been characterized by XRD, TEM and PL spectroscopy. • The crystal structure reveals influence of doping on lattice parameters. • This nanophosphor executes orange–red emission under near UV excitation. - Abstract: BaY{sub 2}ZnO{sub 5}:Sm{sup 3+} nanophosphor was successfully synthesized using solution combustion process. XRD and photoluminescence (PL) techniques were used to analyze the structural and photoluminescence properties. Morphological study of the thermally stable powder was carried out using transmission electron microscope (TEM). Rietveld refinement technique has been used to analyze the samples qualitativelymore » as well as quantitatively. X-Ray diffraction analysis confirms that the highly crystalline single phased Sm{sup 3+} doped BaY{sub 2}ZnO{sub 5} nanophosphor crystallizes in orthorhombic lattice with Pbnm space group. The average particle size lies in the range 80–90 nm with spherical morphology. The photoluminescence excitation at 411 nm yields an intense orange–red emission centered at 610 nm due to {sup 4}G{sub 5/2}–{sup 6}H{sub 7/2} transition. The concentration dependent luminescent behavior of BaY{sub 2(1−x)}Sm{sub 2x}ZnO{sub 5} nanophosphor shows that the optimum concentration for best luminescence is 3 mol%. These results indicate that these nanophosphors find potential applications in the field of phosphor-converted white LED systems.« less

Atomic resolution crystal structure of VcLMWPTP-1 from Vibrio cholerae O395: Insights into a novel mode of dimerization in the low molecular weight protein tyrosine phosphatase family

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nath, Seema; Banerjee, Ramanuj; Sen, Udayaditya, E-mail: udayaditya.sen@saha.ac.in

Highlights: • VcLMWPTP-1 forms dimer in solution. • The dimer is catalytically active unlike other reported dimeric LMWPTPs. • The formation of extended dimeric surface excludes the active site pocket. • The surface bears closer resemblance to eukaryotic LMWPTPs. - Abstract: Low molecular weight protein tyrosine phosphatase (LMWPTP) is a group of phosphotyrosine phosphatase ubiquitously found in a wide range of organisms ranging from bacteria to mammals. Dimerization in the LMWPTP family has been reported earlier which follows a common mechanism involving active site residues leading to an enzymatically inactive species. Here we report a novel form of dimerization inmore » a LMWPTP from Vibrio cholera 0395 (VcLMWPTP-1). Studies in solution reveal the existence of the dimer in solution while kinetic study depicts the active form of the enzyme. This indicates that the mode of dimerization in VcLMWPTP-1 is different from others where active site residues are not involved in the process. A high resolution (1.45 Å) crystal structure of VcLMWPTP-1 confirms a different mode of dimerization where the active site is catalytically accessible as evident by a tightly bound substrate mimicking ligand, MOPS at the active site pocket. Although being a member of a prokaryotic protein family, VcLMWPTP-1 structure resembles very closely to LMWPTP from a eukaryote, Entamoeba histolytica. It also delineates the diverse surface properties around the active site of the enzyme.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miles, Andrew J.; Fedosova, Natalya U.; Hoffmann, Søren V.

Highlights: •Ouabain binding to pig and shark Na,K-ATPase enhances thermal stability. •Ouabain stabilises both membrane-bound and solubilised Na,K-ATPase. •Synchrotron radiation circular dichroism is used for structure determination. •Secondary structure in general is not affected by ouabain binding. •Stabilisation is due to re-arrangement of tertiary structure. -- Abstract: Cardiotonic steroids such as ouabain bind with high affinity to the membrane-bound cation-transporting P-type Na,K-ATPase, leading to complete inhibition of the enzyme. Using synchrotron radiation circular dichroism spectroscopy we show that the enzyme-ouabain complex is less susceptible to thermal denaturation (unfolding) than the ouabain-free enzyme, and this protection is observed with Na,K-ATPase purifiedmore » from pig kidney as well as from shark rectal glands. It is also shown that detergent-solubilised preparations of Na,K-ATPase are stabilised by ouabain, which could account for the successful crystallisation of Na,K-ATPase in the ouabain-bound form. The secondary structure is not significantly affected by the binding of ouabain. Ouabain appears however, to induce a reorganization of the tertiary structure towards a more compact protein structure which is less prone to unfolding; recent crystal structures of the two enzymes are consistent with this interpretation. These circular dichroism spectroscopic studies in solution therefore provide complementary information to that provided by crystallography.« less